TWI583481B

TWI583481B - A method of forming a solder composition

Info

Publication number: TWI583481B
Application number: TW104123697A
Authority: TW
Inventors: 潔妮Ｓ黃; 約翰皮萊拉; 亞歷山德拉Ｍ麥金; 約瑟夫Ｃ剛薩維司
Original assignee: 安塔雅科技公司
Priority date: 2011-02-04
Filing date: 2012-02-03
Publication date: 2017-05-21
Also published as: US20180207753A1; US20120222893A1; TW201238696A; CN103476539A; JP2014509944A; BR112013019849A2; EP2990155A1; US8771592B2; EP2670560B1; JP6928062B2; MX356849B; TWI642510B; JP6243893B2; JP6846328B2; MX344239B; PL2990155T3; JP2016052684A; CN103476539B; WO2012106434A1; EP2990155B1

Description

形成焊料組成物之方法 Method of forming a solder composition

【相關申請案】[related application]

本申請案主張2011年2月4日申請之美國臨時申請案第61/439,538號及2011年9月28日申請之美國臨時申請案第61/540,213號之權利。以上申請案之全部教示係以引用之方式併入本文中。 The present application claims the benefit of U.S. Provisional Application No. 61/439,538, filed on Feb. 4, 2011, and U.S. Provisional Application Serial No. 61/540,213, filed on Sep. 28, 2011. All teachings of the above application are hereby incorporated by reference.

本發明係關於一種焊料組成物。 This invention relates to a solder composition.

車輛(諸如汽車)之前窗及後窗通常包括位於玻璃內或位於玻璃上的電子元件。典型地，電子元件為天線或除霜器。為了向該電子元件提供電連接，向玻璃塗覆較小區域之金屬塗層以製得與電子元件電連接之金屬化表面。隨後，將電連接器焊接於金屬化表面上。通常用含鉛(Pb)焊料將電(亦即電源)連接器焊接至玻璃之金屬化表面上。由於各個國家對環境之關注及/或法規要求，故大多數產業目前在焊接應用中使用或計劃使用無鉛焊料。一些產業中所用的常見無鉛焊料含有較高錫(Sn)含量，諸如大於80%錫。如本文中所描述之汽車玻璃上所用的無鉛焊料揭示於在2001年7月3日頒予John Pereira之美國專利第6,253,988號中(下文中稱為「Pereira」)。在數種無鉛焊料中，Pereira揭示一種具有64.35重量%至65.65重量%銦(In)、29.7重量%至30.3重量%錫(Sn)、4.05重量%至4.95重量% 銀(Ag)、0.25重量%至0.75重量%銅(Cu)之焊料組成物(下文中稱為「65銦焊料(65 Indium Solder)」)。 Front and rear windows of vehicles, such as automobiles, typically include electronic components located within or on the glass. Typically, the electronic component is an antenna or a defroster. To provide an electrical connection to the electronic component, a thin metal coating is applied to the glass to produce a metallized surface that is electrically connected to the electronic component. Subsequently, the electrical connector is soldered to the metallized surface. The electrical (ie, power) connector is typically soldered to the metallized surface of the glass using lead (Pb) solder. Due to environmental concerns and/or regulatory requirements in various countries, most industries currently use or plan to use lead-free solder in soldering applications. Common lead-free solders used in some industries contain higher tin (Sn) content, such as greater than 80% tin. A lead-free solder for use on automotive glass as described herein is disclosed in U.S. Patent No. 6,253,988 (hereinafter referred to as "Pereira") issued to John Pereira on July 3, 2001. Among several lead-free solders, Pereira discloses a type having 64.35 wt% to 65.65 wt% indium (In), 29.7% wt% to 30.3 wt% tin (Sn), 4.05 wt% to 4.95 wt%. Silver (Ag), a solder composition of 0.25 wt% to 0.75 wt% copper (Cu) (hereinafter referred to as "65 Indium Solder").

當將元件焊接至汽車玻璃上時，遭遇到在其他應用中所不存在的困難。汽車玻璃易碎且通常錫含量較高，適用於其他應用之無鉛焊料可典型地致使汽車玻璃開裂。儘管諸如陶瓷及矽之材料可能似乎在某些方面與汽車玻璃類似，但適用於焊接陶瓷或矽元件之一些焊料不適用於焊接至汽車玻璃上。焊接兩種在熱膨脹係數(CTE)方面具有實質性差異的材料(在此情形中諸如玻璃及銅)，在焊點冷卻期間或在後續溫度偏離期間對焊料施加應力。焊料組成物需要具有足夠低的熔點(液相線)從而不會在焊接製程期間導致汽車玻璃開裂，此係因為較高熔點及相應較高的處理溫度增強CTE失配之不利效應，在冷卻期間施加較高應力。然而，焊料組成物之熔點需要足夠高以便在汽車正常使用期間(例如當汽車在太陽下車窗接近太陽或在其他極端惡劣環境條件下時)不會熔融。然而，含銦焊料通常比其他焊料具有低得多的熔點。舉例而言，65銦焊料與鉛焊料160℃相比具有109℃之固相線溫度，且與鉛焊料224℃相比具有127℃之液相線溫度。一些車輛製造商需要將能夠經受得住高溫(例如對於一個原始設備製造商(OEM)為110℃且對於另一者為120℃)且在性能方面無任何劣化的玻璃製品。 When the component is soldered to the automotive glass, difficulties that are not present in other applications are encountered. Automotive glass is fragile and typically has a high tin content, and lead-free solders suitable for other applications typically cause cracking of automotive glass. While materials such as ceramics and tantalum may appear similar in some respects to automotive glass, some solders suitable for soldering ceramic or tantalum components are not suitable for soldering to automotive glass. Two materials that have substantial differences in coefficient of thermal expansion (CTE), such as glass and copper, are welded, stress is applied to the solder during solder joint cooling or during subsequent temperature deviations. The solder composition needs to have a sufficiently low melting point (liquidus) so as not to cause cracking of the automotive glass during the soldering process, because the higher melting point and correspondingly higher processing temperatures enhance the adverse effects of CTE mismatch during cooling Apply a higher stress. However, the melting point of the solder composition needs to be high enough to not melt during normal use of the vehicle (eg, when the car is approaching the sun in the sun or under other extreme environmental conditions). However, indium containing solders typically have a much lower melting point than other solders. For example, 65 indium solder has a solidus temperature of 109 ° C compared to lead solder at 160 ° C and a liquidus temperature of 127 ° C compared to lead solder 224 ° C. Some vehicle manufacturers require glass articles that can withstand high temperatures (eg, 110 ° C for one original equipment manufacturer (OEM) and 120 ° C for the other) without any degradation in performance.

因此，存在對適用於玻璃之相較於目前可用組成物可經受更高高溫同時提供此應用領域之所有其他所需性質之無鉛焊料組成物的需要。 Accordingly, a need exists for a lead-free solder composition suitable for use in glass that can withstand higher temperatures than currently available compositions while providing all of the other desirable properties of this application.

本發明一般係關於一種焊料組成物。 The present invention generally relates to a solder composition.

一個具體實例包括約4重量%至約25重量%錫、約0.1重量 %至約8重量%銻、約0.03重量%至約4重量%銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀。焊料組成物可具有範圍在介於約120℃和約145℃之間的固相線溫度及範圍在介於130℃和約155℃之間的液相線溫度。 A specific example includes from about 4% by weight to about 25% by weight tin, about 0.1 weight % to about 8 wt% 锑, about 0.03 wt% to about 4 wt% copper, about 0.03 wt% to about 4 wt% nickel, about 66 wt% to about 90 wt% indium, and about 0.5 wt% to about 9 wt% silver. The solder composition can have a solidus temperature ranging between about 120 °C and about 145 °C and a liquidus temperature ranging between 130 °C and about 155 °C.

在某些具體實例中，組成物另外包括約0.2重量%至約6重量%鋅。在某些其他具體實例中，組成物另外包括約0.01重量%至約0.3重量%鍺。在此等特定具體實例中，組成物可包括約70重量%至約86重量%銦。 In certain embodiments, the composition additionally includes from about 0.2% to about 6 weights Amount of zinc. In certain other embodiments, the composition additionally includes from about 0.01% to about 0.3% by weight hydrazine. In these particular embodiments, the composition can include from about 70% to about 86% by weight indium.

在一些具體實例中，組成物包括約7重量%至約19重量% 錫、約0.2重量%至約8重量%銻、約0.1重量%至約1.5重量%銅、約0.1重量%至約4重量%鎳、約70重量%至約80重量%銦及約4重量%至約8重量%銀。 In some embodiments, the composition comprises from about 7 wt% to about 19 wt% Tin, from about 0.2% to about 8% by weight cerium, from about 0.1% to about 1.5% by weight copper, from about 0.1% to about 4% by weight nickel, from about 70% to about 80% by weight indium, and about 4% by weight Up to about 8 wt% silver.

在一些其他具體實例中，組成物包括約4重量%至約20重量%錫、約0.1重量%至約8重量%銻、約0.1重量%至約4重量%銅、約0.1重量%至約3重量%鎳、約71重量%至約86重量%銦及約1重量%至約6重量%銀。 In some other specific examples, the composition comprises from about 4% to about 20 weights Amounts of tin, from about 0.1% to about 8% by weight, from about 0.1% to about 4% by weight copper, from about 0.1% to about 3% by weight nickel, from about 71% to about 86% by weight indium and about 1 From % by weight to about 6% by weight of silver.

在其他具體實例中，組成物包括約11重量%至約17重量% 錫、約0.5重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約5重量%鎳、約72重量%至約77重量%銦、約4重量%至約8.5重量%銀及約0.3重量%至約1.5重量%鋅。在此等特定具體實例中，組成物可包括約13重量%至約15重量%錫、約0.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%至約4重量%鎳、約74重量%至約75重量%銦、約5重量%至約8.5重量%銀及約0.3重量%至約1.5重量%鋅。此等特定具體實例之實例可包括約15重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約0.5重量%至約1.5重量%鋅，諸如約15重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約1重量%鋅。此等特定具體實例之其他實例可包括約14重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約14重量%錫、約1重量%銻、約1重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約1重量%鋅。此等特定具體實例之其他實例可包括約13重量%錫、約1.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約13重量%錫、約2重量%銻、約1重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約1重量%鋅。 In other embodiments, the composition comprises from about 11% to about 17% by weight Tin, from about 0.5% to about 3% by weight bismuth, from about 0.5% to about 1.5% by weight copper, from about 0.5% to about 5% by weight nickel, from about 72% to about 77% by weight indium, about 4% by weight To about 8.5 wt% silver and from about 0.3 wt% to about 1.5 wt% zinc. In these specific examples, the composition It may include from about 13% by weight to about 15% by weight tin, from about 0.5% to about 2.5% by weight bismuth, from about 0.5% to about 1.5% by weight copper, from about 1% to about 4% by weight nickel, about 74% by weight Up to about 75% by weight indium, from about 5% by weight to about 8.5 % by weight silver, and from about 0.3% to about 1.5% by weight zinc. Examples of such specific embodiments may include about 15% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 1% by weight nickel, about 75% by weight indium, about 6 wt% silver and from about 0.5 wt% to about 1.5 wt% zinc, such as about 15 wt% tin, about 1 wt% rhodium, about 1 wt% copper, about 1 wt% nickel, about 75 wt% indium, about 6 wt. % silver and about 1% by weight zinc. Other examples of such specific embodiments can include about 14% tin by weight, about 0.5% to about 1.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 3% by weight nickel, about 75% by weight indium, About 5% by weight of silver and about 0.5% to about 1.5% by weight of zinc, such as about 14% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 3% by weight nickel, about 75% by weight indium, about 5 Weight % silver and about 1% by weight zinc. Other examples of such specific embodiments may include about 13% by weight tin, about 1.5% to about 2.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 4% by weight nickel, about 74% by weight indium, About 5 wt% silver and about 0.5 wt% to about 1.5 wt% zinc, such as about 13 wt% tin, about 2 wt% rhodium, about 1 wt% copper, about 4 wt% nickel, about 74 wt% indium, about 5 Weight % silver and about 1% by weight zinc.

在其他具體實例中，組成物基本上由以下組成：約11重量 %至約17重量%錫、約0.5重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約5重量%鎳、約72重量%至約77重量%銦、約4重量%至約8.5重量%銀及約0.3重量%至約1.5重量%鋅。在此等特定具體實例中，組成物基本上可由以下組成：約13重量%至約15重量%錫、約0.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%至約4 重量%鎳、約74重量%至約75重量%銦、約5重量%至約8.5重量%銀及約0.3重量%至約1.5重量%鋅。此等特定具體實例之實例基本上可由以下組成：約15重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約0.5重量%至約1.5重量%鋅，諸如約15重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約1重量%鋅。此等特定具體實例之其他實例基本上可由以下組成：約14重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約14重量%錫、約1重量%銻、約1重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約1重量%鋅。此等特定具體實例之其他實例基本上可由以下組成：約13重量%錫、約1.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約13重量%錫、約2重量%銻、約1重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約1重量%鋅。在此等特定具體實例中，焊料組成物可具有範圍在介於約120℃和約145℃之間、諸如範圍在介於約120℃和約135℃之間的固相線溫度及範圍在介於130℃和約155℃之間、諸如範圍在介於約130℃和約145℃之間的液相線溫度。 In other embodiments, the composition consists essentially of: about 11 weight % to about 17% by weight tin, about 0.5% to about 3% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 0.5% to about 5% by weight nickel, about 72% to about 77% by weight Indium, from about 4% by weight to about 8.5% by weight silver and from about 0.3% by weight to about 1.5% by weight zinc. In these particular embodiments, the composition can consist essentially of from about 13% to about 15% tin, from about 0.5% to about 2.5% by weight, from about 0.5% to about 1.5% by weight copper, about 1% by weight to about 4 Weight% nickel, from about 74% to about 75% by weight indium, from about 5% to about 8.5% by weight silver, and from about 0.3% to about 1.5% by weight zinc. Examples of such specific embodiments can consist essentially of: about 15% by weight tin, about 0.5% to about 1.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 1% by weight nickel, about 75 weight % indium, about 6% by weight silver, and about 0.5% to about 1.5% by weight zinc, such as about 15% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 75% by weight indium About 6% by weight of silver and about 1% by weight of zinc. Other examples of such specific embodiments can consist essentially of: about 14% by weight tin, about 0.5% to about 1.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 3% by weight nickel, about 75 Weight % indium, about 5% by weight silver, and about 0.5% to about 1.5% by weight zinc, such as about 14% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 3% by weight nickel, about 75% by weight Indium, about 5% by weight silver, and about 1% zinc by weight. Other examples of such specific embodiments can consist essentially of: about 13% by weight tin, about 1.5% to about 2.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 4% by weight nickel, about 74% Weight % indium, about 5% by weight silver, and about 0.5% to about 1.5% by weight zinc, such as about 13% by weight tin, about 2% by weight bismuth, about 1% by weight copper, about 4% by weight nickel, about 74% by weight Indium, about 5% by weight silver, and about 1% zinc by weight. In these particular embodiments, the solder composition can have a solidus temperature and range ranging between about 120 ° C and about 145 ° C, such as between about 120 ° C and about 135 ° C. A liquidus temperature between 130 ° C and about 155 ° C, such as between about 130 ° C and about 145 ° C.

本發明亦係關於一種玻璃組件上之電連接，其包括玻璃組件、玻璃組件上含有銀的電接點表面及用焊料組成物層焊接至玻璃組件上之電接點表面的電連接器，該焊料組成物具有包含以下之元素混合物：約4重量%至約25重量%錫、約0.1重量%至約8重量%銻、約0.03重量%至約4 重量%銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀。在其他具體實例中，玻璃組件上之電連接包括玻璃組件、玻璃組件上含有銀的電接點表面及用焊料組成物層焊接至玻璃組件上之電接點表面的電連接器，該焊料組成物基本上由以下組成：約4重量%至約25重量%錫、約0.1重量%至約8重量%銻、約0.03重量%至約4重量%銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀。 The invention also relates to an electrical connection on a glass component, comprising a glass set An electrical contact surface comprising silver on the glass component and an electrical connector soldered to the surface of the electrical contact on the glass component, the solder composition having a mixture of elements comprising: about 4% by weight to about 25 wt% tin, from about 0.1 wt% to about 8 wt% 锑, from about 0.03 wt% to about 4 The weight percent copper, from about 0.03 wt% to about 4 wt% nickel, from about 66 wt% to about 90 wt% indium, and from about 0.5 wt% to about 9 wt% silver. In other embodiments, the electrical connection on the glass component includes a glass component, an electrical contact surface containing silver on the glass component, and an electrical connector soldered to the surface of the electrical contact on the glass component with a solder composition layer. The composition consists essentially of from about 4% by weight to about 25% by weight tin, from about 0.1% by weight to about 8% by weight bismuth, from about 0.03% by weight to about 4% by weight copper, from about 0.03% by weight to about 4% by weight nickel. From about 66% by weight to about 90% by weight indium and from about 0.5% to about 9% by weight silver.

本發明亦係關於一種形成焊料組成物之方法，其包括將銦、鎳、銅、銀、銻及錫混合在一起形成包括約4重量%至約25重量%錫、約0.1重量%至約8重量%銻、約0.03重量%至約4重量%銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀的合金。在一些具體實例中，銦與錫一起混合於第一熔融混合物中，且至少鎳、銅及銀於溶液中一起混合於添加至第一熔融混合物中的第二混合物中。在其他具體實例中，錫與鎳一起混合於熔融混合物中，且隨後將至少銅、銦及銀添加至熔融混合物中。在此等特定具體實例中，可在已將所有其他金屬添加至熔融混合物中之後添加鋅。 The invention also relates to a method of forming a solder composition comprising indium, Nickel, copper, silver, lanthanum and tin are mixed together to form from about 4% to about 25% by weight tin, from about 0.1% to about 8% by weight cerium, from about 0.03% to about 4% by weight copper, about 0.03 by weight An alloy of from about 4% by weight nickel, from about 66% by weight to about 90% by weight indium, and from about 0.5% by weight to about 9% by weight silver. In some embodiments, indium is mixed with tin in the first molten mixture, and at least nickel, copper, and silver are mixed together in solution in the second mixture added to the first molten mixture. In other embodiments, tin is mixed with nickel in the molten mixture, and then at least copper, indium, and silver are added to the molten mixture. In these particular embodiments, zinc may be added after all other metals have been added to the molten mixture.

在一些具體實例中，錫以約7重量%至約19重量%之比例混合、銻以約0.2重量%至約8重量%之比例混合、銅以約0.1重量%至約1.5重量%之比例混合、鎳以約0.1重量%至約4重量%之比例混合、銦以約70重量%至約80重量%之比例混合且銀以約4重量%至約8重量%之比例混合。 In some embodiments, tin is mixed in a ratio of from about 7% by weight to about 19% by weight. The mixture is mixed in a ratio of about 0.2% by weight to about 8% by weight, the copper is mixed in a ratio of about 0.1% by weight to about 1.5% by weight, and the nickel is mixed in a ratio of about 0.1% by weight to about 4% by weight. The ratio of 70% by weight to about 80% by weight is mixed and the silver is mixed in a ratio of about 4% by weight to about 8% by weight.

在其他具體實例中，一種形成焊料組成物之方法，其包括將銦、鎳、銅、鋅、銀、銻及錫混合在一起形成包括約11重量%至約17重量 %錫、約0.5重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約5重量%鎳、約72重量%至約77重量%銦、約4重量%至約8重量%銀及約0.5重量%至約1.5重量%鋅的合金。在此等特定具體實例中，組成物可包括約13重量%至約15重量%錫、約0.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%至約4重量%鎳、約74重量%至約75重量%銦、約5重量%至約6重量%銀及約0.5重量%至約1.5重量%鋅。此等特定具體實例之實例可包括約15重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約0.5重量%至約1.5重量%鋅，諸如約15重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約1重量%鋅。此等特定具體實例之其他實例可包括約14重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約14重量%錫、約1重量%銻、約1重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約1重量%鋅。此等特定具體實例之其他實例可包括約13重量%錫、約1.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約13重量%錫、約2重量%銻、約1重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約1重量%鋅。 In other embodiments, a method of forming a solder composition, including Indium, nickel, copper, zinc, silver, antimony and tin are mixed together to form from about 11% by weight to about 17% by weight. % tin, from about 0.5% by weight to about 3% by weight bismuth, from about 0.5% by weight to about 1.5% by weight copper, from about 0.5% by weight to about 5% by weight nickel, from about 72% by weight to about 77% by weight indium, about 4 parts by weight % to about 8 wt% silver and an alloy of from about 0.5 wt% to about 1.5 wt% zinc. In these particular embodiments, the composition can include from about 13% to about 15% tin, from about 0.5% to about 2.5% by weight cerium, from about 0.5% to about 1.5% by weight copper, from about 1% to about About 4% by weight nickel, about 74% by weight to about 75% by weight indium, about 5% by weight to about 6% by weight silver, and about 0.5% by weight to about 1.5% by weight zinc. Examples of such specific embodiments may include about 15% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 1% by weight nickel, about 75% by weight indium, about 6 wt% silver and from about 0.5 wt% to about 1.5 wt% zinc, such as about 15 wt% tin, about 1 wt% rhodium, about 1 wt% copper, about 1 wt% nickel, about 75 wt% indium, about 6 wt. % silver and about 1% by weight zinc. Other examples of such specific embodiments can include about 14% tin by weight, about 0.5% to about 1.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 3% by weight nickel, about 75% by weight indium, About 5% by weight of silver and about 0.5% to about 1.5% by weight of zinc, such as about 14% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 3% by weight nickel, about 75% by weight indium, about 5 Weight % silver and about 1% by weight zinc. Other examples of such specific embodiments may include about 13% by weight tin, about 1.5% to about 2.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 4% by weight nickel, about 74% by weight indium, About 5 wt% silver and about 0.5 wt% to about 1.5 wt% zinc, such as about 13 wt% tin, about 2 wt% rhodium, about 1 wt% copper, about 4 wt% nickel, about 74 wt% indium, about 5 Weight % silver and about 1% by weight zinc.

除提供環境友好的無鉛材料以外，本發明之焊料組成物具有許多優點，諸如提供可用於汽車玻璃之無鉛組成物，在強度及延性方面提供必需的機械性質且經受所需較高操作溫度，同時保留所需較低製造製程溫度。 In addition to providing an environmentally friendly lead-free material, the solder composition of the present invention has Many advantages, such as providing lead-free compositions that can be used in automotive glass, provide the necessary mechanical properties in terms of strength and ductility and withstand the higher operating temperatures required while retaining the lower manufacturing processes required temperature.

10‧‧‧後窗 10‧‧‧ Rear window

12‧‧‧風窗除霜器 12‧‧‧wind window defroster

14‧‧‧除霜線 14‧‧‧Defrost line

16‧‧‧電接點條 16‧‧‧Electrical contact strips

18‧‧‧電連接器 18‧‧‧Electrical connector

18a‧‧‧橋連端點電力連接器 18a‧‧‧Bridged Endpoint Power Connectors

18b‧‧‧橋連端點電力連接器 18b‧‧‧Bridged Endpoint Power Connectors

19‧‧‧焊料墊 19‧‧‧ solder pads

20‧‧‧焊料組成物 20‧‧‧ solder composition

22‧‧‧電力線 22‧‧‧Power line

300‧‧‧拉力測試 300‧‧‧ Rally test

310‧‧‧數位測力計 310‧‧‧Digital dynamometer

320‧‧‧鉤 320‧‧‧ hook

330‧‧‧手柄 330‧‧‧handle

400‧‧‧測試 400‧‧‧Test

410‧‧‧連接的砝碼 410‧‧‧Connected weights

420‧‧‧鉤 420‧‧‧ hook

430‧‧‧熱電偶 430‧‧‧ thermocouple

圖1為包括電動操作除霜器之汽車後窗的內視圖。 1 is an internal view of a rear window of a vehicle including an electrically operated defroster.

圖2為焊接至圖1之後窗電接點上之電連接器的側視圖，其中後窗、電接點及焊料以剖面展示。 2 is a side elevational view of the electrical connector soldered to the electrical contacts of the window of FIG. 1, with the rear window, electrical contacts, and solder shown in cross section.

圖3A為形成本發明中焊料組成物之具體實例的一方法之流程圖之示意圖。 Fig. 3A is a schematic view showing a flow chart of a method of forming a specific example of the solder composition of the present invention.

圖3B為形成本發明中焊料組成物之具體實例的另一方法之流程圖之示意圖。 Fig. 3B is a schematic view showing a flow chart of another method of forming a specific example of the solder composition of the present invention.

圖4A及圖4B為可用本發明之焊料組成物焊接的電力連接器之示意圖。 4A and 4B are schematic views of a power connector solderable using the solder composition of the present invention.

圖5為用本發明之焊料組成物焊接於前窗上的電力連接器之示意圖。 Figure 5 is a schematic illustration of a power connector soldered to a front window using a solder composition of the present invention.

圖6為使用本發明之焊料組成物之前窗總成的示意圖。 Figure 6 is a schematic illustration of a window assembly prior to use of the solder composition of the present invention.

圖7為在本發明焊料組成物之具體實例的溫度循環測試之一個循環期間溫度隨時間而變的圖示。 Figure 7 is a graphical representation of temperature as a function of time during one cycle of a temperature cycling test of a specific example of a solder composition of the present invention.

圖8為使用測力計測試本發明焊料組成物之性能的拉力測試之示意圖。 Figure 8 is a schematic illustration of a tensile test using a dynamometer to test the properties of the solder composition of the present invention.

圖9為使用砝碼測試本發明焊料組成物之性能的拉力測試之示意圖。 Figure 9 is a schematic illustration of a tensile test using the weight to test the properties of the solder composition of the present invention.

自如在隨附圖式(其中同樣的參考字符在不同視圖中指代相同零件)中說明的本發明之例示具體實例之以下更特定描述將顯而易知前述內容。圖式未必按比例繪製，而是著重在於說明本發明之具體實例。 The foregoing is more readily apparent from the following detailed description of the exemplary embodiments of the invention illustrated in the accompanying drawings. The drawings are not necessarily drawn to scale, but rather to illustrate specific embodiments of the invention.

本發明提供一種適用於將電子組件焊接至玻璃上以便與玻璃內或玻璃上之電子元件電連接的焊料組成物。參照圖1，採用汽車之後窗10(例如在歐洲亦稱為背光(backlight))作為說明性實例。窗(玻璃組件)10包括由嵌入窗10內或沈積於窗10內表面上之電阻性除霜線14組成的風窗除霜器12。除霜線14與位於窗10之內表面上的一對電接點條(電接點表面，亦稱為匯流條)16電連接。電接點條16由沈積於窗10之內表面上的導電塗層組成。典型地，電接點條16由含銀材料形成。 The present invention provides a method for soldering electronic components to glass for use with glass A solder composition in which the electronic components in the glass or the glass are electrically connected. Referring to Figure 1, a rear window 10 of a vehicle (e.g., also referred to as backlight in Europe) is employed as an illustrative example. The window (glass assembly) 10 includes a windshield defroster 12 comprised of a resistive defroster line 14 embedded in the window 10 or deposited on the inner surface of the window 10. The defroster line 14 is electrically coupled to a pair of electrical contact strips (electrical contact surfaces, also referred to as bus bars) 16 located on the inner surface of the window 10. The electrical contact strip 16 is comprised of a conductive coating deposited on the inner surface of the window 10. Typically, the electrical contact strips 16 are formed from a silver-containing material.

當將元件焊接至汽車玻璃上時，遭遇到在其他應用中所不存在的困難。為了解決原始設備製造商(OEM)關於在汽車玻璃上使用無鉛焊料的一些顧慮，汽車玻璃供應商(諸如CLEPA(歐洲汽車供應商協會))已開發數種測試，包括溫度週期變化、持續頂點濕度、頂點溫度與濕度及高溫儲存。為了解決OEM對焊料熔點之顧慮，一個測試包括用65銦焊料焊接至連接器上之在105℃下儲存500小時的玻璃樣品，在儲存期間將500公克砝碼懸掛於各連接器上，但在測試期間連接器未自玻璃脫離。然而，OEM(諸如歐洲汽車製造商協會(ACEA))提出溫度可高達115℃至120℃。 When the component is soldered to the automotive glass, it does not exist in other applications. The difficulty in it. In order to address some of the concerns of original equipment manufacturers (OEMs) about the use of lead-free solder on automotive glass, automotive glass suppliers such as CLEPA (European Association of Automotive Suppliers) have developed several tests, including temperature cycle variations, continuous peak humidity. , peak temperature and humidity and high temperature storage. In order to address OEM concerns about solder melting point, one test included a glass sample stored at 105 ° C for 500 hours with 65 indium solder soldered to the connector, and a 500 gram weight was suspended from each connector during storage, but The connector did not detach from the glass during the test. However, OEMs such as the European Automobile Manufacturers Association (ACEA) have suggested temperatures up to 115 ° C to 120 ° C.

開發本發明之焊料組成物來解決OEM之上述顧慮。參照圖 2，使用標準焊接技術(諸如電阻焊接元件或火焰、微火焰、熱鐵、熱空氣及感應加熱)採用本發明之焊料組成物層20將電(亦即電力)連接器18焊接至窗10上的各電接點條(亦即匯流條)16上。焊接可在環境空氣氛圍中進行，無需惰性氣體環境。隨後，電力線22可與電連接器18電連接以向風窗除霜器12(圖1)提供電力。以下提供焊料性能測試及結果。 The solder composition of the present invention was developed to address the above concerns of OEMs. Reference map 2. Welding of the electrical (i.e., electrical) connector 18 to the window 10 using the solder composition layer 20 of the present invention using standard soldering techniques such as resistance welding elements or flame, micro-flame, hot iron, hot air, and induction heating. Each electrical contact strip (ie, bus bar) 16 is on. Welding can be carried out in an ambient air atmosphere without the need for an inert gas atmosphere. Power line 22 can then be electrically coupled to electrical connector 18 to provide power to windshield defroster 12 (FIG. 1). Solder performance tests and results are provided below.

在一個具體實例中，本發明焊料組成物20包括約4重量% 至約25重量%錫、約0.1重量%至約8重量%銻、約0.03重量%至約4重量 %銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀。 In one embodiment, the solder composition 20 of the present invention comprises about 4% by weight. Up to about 25 wt% tin, from about 0.1 wt% to about 8 wt% 锑, from about 0.03 wt% to about 4 wt% % copper, from about 0.03 wt% to about 4 wt% nickel, from about 66 wt% to about 90 wt% indium, and from about 0.5 wt% to about 9 wt% silver.

在一些具體實例中，組成物20包括約1重量%至約7重量% 銀。在某些具體實例中，組成物20包括約0.2重量%至約8重量%銻。在其他具體實例中，組成物20包括約3重量%至約7重量%銀。在其他具體實例中，組成物20包括約1重量%至約4重量%銀。 In some embodiments, composition 20 includes from about 1% to about 7% by weight. silver. In certain embodiments, composition 20 includes from about 0.2% to about 8% by weight hydrazine. In other embodiments, composition 20 includes from about 3% by weight to about 7% by weight silver. In other embodiments, composition 20 includes from about 1% to about 4% silver by weight.

在某些具體實例中，組成物20另外包括約0.2重量%至約6 重量%鋅。在某些其他具體實例中，組成物20另外包括約0.3重量%至約6重量%鋅。在其他具體實例中，組成物20另外包括約3重量%至約5重量%鋅。 In certain embodiments, composition 20 additionally includes from about 0.2% to about 6 Weight% zinc. In certain other specific examples, composition 20 additionally includes from about 0.3% to about 6% by weight zinc. In other embodiments, composition 20 additionally includes from about 3% by weight to about 5% by weight zinc.

在某些其他具體實例中，組成物20另外包括約0.01重量% 至約0.3重量%鍺。在此等特定具體實例中，組成物20可包括約70重量%至約86重量%銦。 In certain other specific examples, composition 20 additionally includes about 0.01% by weight Up to about 0.3% by weight 锗. In these particular embodiments, composition 20 can include from about 70% to about 86% by weight indium.

在一些具體實例中，組成物20包括約7重量%至約19重量 %錫、約0.2重量%至約8重量%銻、約0.1重量%至約1.5重量%銅、約0.1重量%至約4重量%鎳、約70重量%至約80重量%銦及約4重量%至約8重量%銀。 In some embodiments, composition 20 comprises from about 7% by weight to about 19 weight. % tin, from about 0.2% by weight to about 8% by weight bismuth, from about 0.1% by weight to about 1.5% by weight copper, from about 0.1% by weight to about 4% by weight nickel, from about 70% by weight to about 80% by weight of indium and about 4 parts by weight % to about 8 wt% silver.

在某些具體實例中，組成物20包括約74重量%至約78重量%銦。在此等特定具體實例中，組成物20可包括約5重量%至約10重量%錫或約12重量%至約19重量%錫或約12重量%至約16重量%錫。在某些其他具體實例中，組成物20包括約74重量%至約80重量%銦。在其他具體實例中，組成物20包括約0.1重量%至約3重量%鎳。在其他具體實例中，組成物20包括約0.2重量%至約5重量%銻。 In certain embodiments, composition 20 includes from about 74% to about 78 weight Amount of indium. In these particular embodiments, composition 20 can include from about 5% by weight to about 10% by weight tin or from about 12% to about 19% by weight tin or from about 12% to about 16% by weight tin. In certain other specific examples, composition 20 includes from about 74% to about 80% by weight indium. In other embodiments, composition 20 includes from about 0.1% to about 3% by weight nickel. In other specific examples, Composition 20 includes from about 0.2% to about 5% by weight bismuth.

在其他具體實例中，組成物20包括約11重量%至約17重量%錫、約0.5重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約5重量%鎳、約72重量%至約77重量%銦、約4重量%至約7重量%銀及約0.5重量%至約1.5重量%鋅。在此等特定具體實例中，組成物20可包括約13重量%至約15重量%錫、約0.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%至約4重量%鎳、約74重量%至約75重量%銦、約5重量%至約6重量%銀及約0.5重量%至約1.5重量%鋅。此等特定具體實例之實例可包括約15重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約0.5重量%至約1.5重量%鋅，諸如約15重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦、約6重量%銀及約1重量%鋅。此等特定具體實例之其他實例可包括約14重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約14重量%錫、約1重量%銻、約1重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約1重量%鋅。此等特定具體實例之其他實例可包括約13重量%錫、約1.5重量%至約2.5重量%銻、約0.5重量%至約1.5重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約0.5重量%至約1.5重量%鋅，諸如約13重量%錫、約2重量%銻、約1重量%銅、約4重量%鎳、約74重量%銦、約5重量%銀及約1重量%鋅。 In other embodiments, composition 20 includes from about 11% to about 17 weights Amounts of tin, from about 0.5% to about 3% by weight cerium, from about 0.5% to about 1.5% by weight copper, from about 0.5% to about 5% by weight nickel, from about 72% to about 77% by weight indium, about 4 From % by weight to about 7% by weight silver and from about 0.5% by weight to about 1.5% by weight zinc. In these particular embodiments, composition 20 can include from about 13% to about 15% tin, from about 0.5% to about 2.5% by weight, from about 0.5% to about 1.5% copper, about 1% by weight. Up to about 4% by weight nickel, from about 74% to about 75% by weight indium, from about 5% to about 6% by weight silver, and from about 0.5% to about 1.5% by weight zinc. Examples of such specific embodiments may include about 15% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 1% by weight nickel, about 75% by weight indium, about 6 wt% silver and from about 0.5 wt% to about 1.5 wt% zinc, such as about 15 wt% tin, about 1 wt% rhodium, about 1 wt% copper, about 1 wt% nickel, about 75 wt% indium, about 6 wt. % silver and about 1% by weight zinc. Other examples of such specific embodiments can include about 14% tin by weight, about 0.5% to about 1.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 3% by weight nickel, about 75% by weight indium, About 5% by weight of silver and about 0.5% to about 1.5% by weight of zinc, such as about 14% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 3% by weight nickel, about 75% by weight indium, about 5 Weight % silver and about 1% by weight zinc. Other examples of such specific embodiments may include about 13% by weight tin, about 1.5% to about 2.5% by weight bismuth, about 0.5% to about 1.5% by weight copper, about 4% by weight nickel, about 74% by weight indium, About 5 wt% silver and about 0.5 wt% to about 1.5 wt% zinc, such as about 13 wt% tin, about 2 wt% rhodium, about 1 wt% copper, about 4 wt% nickel, about 74 wt% indium, about 5 Weight % silver and about 1% by weight zinc.

焊料組成物20可具有範圍在介於約120℃和約145℃之間的固相線溫度及範圍在介於130℃和約155℃之間的液相線溫度。固相線溫度實際上定義為合金開始熔融之溫度。在固相線溫度以下，物質完全呈固體，無熔融相。液相線溫度為晶體(未熔融金屬或合金)可與熔融物共存的最高溫度。在液相線溫度以上，材料為均質的，僅由熔融物組成。焊料處理溫度高於液相線溫度若干度，該等度數由焊接技術決定。 Solder composition 20 can have a range between about 120 ° C and about 145 ° C. The solidus temperature and range are between liquidus temperatures between 130 °C and about 155 °C. The solidus temperature is actually defined as the temperature at which the alloy begins to melt. Below the solidus temperature, the material is completely solid and has no molten phase. The liquidus temperature is the highest temperature at which crystals (unmelted metals or alloys) can coexist with the melt. Above the liquidus temperature, the material is homogeneous and consists solely of the melt. The solder processing temperature is several degrees above the liquidus temperature, which is determined by the soldering technique.

在一特定具體實例中，組成物20包括約14重量%至約16 重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約74重量%至約76重量%銦及約6重量%至約8重量%銀，諸如約15重量%錫、約1.0重量%銻、約1.0重量%銅、約1.0重量%鎳、約75重量%銦及約7重量%銀。此具體實例中之其他組成物可包括約14重量%至約21重量%錫、約0.2重量%至約3重量%銻、約0.1重量%至約4.0重量%銅、約0.1重量%至約3.0重量%鎳、約72重量%至約80重量%銦及約1重量%至約8重量%銀。 In a particular embodiment, composition 20 comprises from about 14% to about 16% Weight % tin, from about 0.5% to about 1.5% by weight bismuth, from about 0.5% to about 1.5% by weight copper, from about 0.5% to about 1.5% by weight nickel, from about 74% to about 76% by weight indium and about 6 From % by weight to about 8% by weight silver, such as about 15% by weight tin, about 1.0% by weight bismuth, about 1.0% by weight copper, about 1.0% by weight nickel, about 75% by weight indium, and about 7% by weight silver. Other compositions in this particular example may include from about 14% to about 21% by weight tin, from about 0.2% to about 3% by weight bismuth, from about 0.1% to about 4.0% by weight copper, from about 0.1% to about 3.0. Weight% nickel, from about 72% to about 80% by weight indium, and from about 1% to about 8% by weight silver.

在第二特定具體實例中，組成物20包括約14重量%至約16 重量%錫、約2重量%至約4重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約74重量%至約76重量%銦及約4重量%至約6重量%銀，諸如約15重量%錫、約3.0重量%銻、約1.0重量%銅、約1.0重量%鎳、約75重量%銦及約5重量%銀。 In a second specific embodiment, composition 20 comprises from about 14% to about 16 Weight percent tin, from about 2 weight percent to about 4 weight percent rhodium, from about 0.5 wt% to about 1.5 wt% copper, from about 0.5 wt% to about 1.5 wt% nickel, from about 74 wt% to about 76 wt% indium, and about 4 From % by weight to about 6% by weight silver, such as about 15% by weight tin, about 3.0% by weight bismuth, about 1.0% by weight copper, about 1.0% by weight nickel, about 75% by weight indium, and about 5% by weight silver.

在第三特定具體實例中，組成物20包括約12重量%至約14 重量%錫、約2重量%至約4重量%銻、約0.5重量%至約1.5重量%銅、約2重量%至約4重量%鎳、約74重量%至約76重量%銦及約4重量%至約6重量%銀，諸如約13重量%錫、約3.0重量%銻、約1.0重量%銅、約3.0重量%鎳、約75重量%銦及約5重量%銀或約14重量%錫、約3.0重量%銻、約1.0重量%銅、約2.0重量%鎳、約75重量%銦及約5重量%銀。 In a third particular embodiment, composition 20 comprises from about 12% to about 14% Weight percent tin, from about 2 weight percent to about 4 weight percent rhodium, from about 0.5 wt% to about 1.5 wt% copper, from about 2 wt% to about 4 wt% nickel, from about 74 wt% to about 76 wt% indium, and about 4 % by weight to about 6% by weight of silver, such as about 13% by weight tin, about 3.0% by weight bismuth, about 1.0% by weight copper, about 3.0 weight Amounts of nickel, about 75% by weight of indium and about 5% by weight of silver or about 14% by weight of tin, about 3.0% by weight of cerium, about 1.0% by weight of copper, about 2.0% by weight of nickel, about 75% by weight of indium, and about 5% by weight silver.

在第四特定具體實例中，組成物20包括約7重量%至約9 重量%錫、約4重量%至約6重量%銻、約0.5重量%至約1.5重量%銅、約2重量%至約4重量%鎳、約74重量%至約76重量%銦、約4重量%至約6重量%銀及約2重量%至約4重量%鋅，諸如約8重量%錫、約5.0重量%銻、約1.0重量%銅、約3.0重量%鎳、約75重量%銦、約5重量%銀及約3.0重量%鋅。 In a fourth specific embodiment, composition 20 comprises from about 7 wt% to about 9 Weight percent tin, from about 4 weight percent to about 6 weight percent rhodium, from about 0.5 wt% to about 1.5 wt% copper, from about 2 wt% to about 4 wt% nickel, from about 74 wt% to about 76 wt% indium, about 4 From % by weight to about 6% by weight silver and from about 2% by weight to about 4% by weight zinc, such as about 8% by weight tin, about 5.0% by weight bismuth, about 1.0% by weight copper, about 3.0% by weight nickel, about 75% by weight indium About 5% by weight of silver and about 3.0% by weight of zinc.

在第五特定具體實例中，組成物20包括約7重量%至約9 重量%錫、約4重量%至約6重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約74重量%至約76重量%銦、約4重量%至約6重量%銀及約4重量%至約6重量%鋅，諸如約8重量%錫、約5.0重量%銻、約1.0重量%銅、約1.0重量%鎳、約75重量%銦、約5重量%銀及約5.0重量%鋅。 In a fifth specific embodiment, composition 20 comprises from about 7 wt% to about 9 Weight percent tin, from about 4 weight percent to about 6 weight percent rhodium, from about 0.5 wt% to about 1.5 wt% copper, from about 0.5 wt% to about 1.5 wt% nickel, from about 74 wt% to about 76 wt% indium, about 4 Weight% to about 6% by weight silver and from about 4% to about 6% by weight zinc, such as about 8% by weight tin, about 5.0% by weight bismuth, about 1.0% by weight copper, about 1.0% by weight nickel, about 75% by weight indium About 5% by weight of silver and about 5.0% by weight of zinc.

在第六特定具體實例中，組成物20包括約7重量%至約9 重量%錫、約4重量%至約6重量%銻、約0.5重量%至約1.5重量%銅、約2重量%至約4重量%鎳、約74重量%至約76重量%銦、約4重量%至約6重量%銀、約2重量%至約4重量%鋅及約0.05重量%至約0.2重量%鍺，諸如約8重量%錫、約4.9重量%銻、約1.0重量%銅、約3.0重量%鎳、約75重量%銦、約5重量%銀、約3.0重量%鋅及約0.1重量%鍺。 In a sixth specific embodiment, composition 20 comprises from about 7 wt% to about 9 Weight percent tin, from about 4 weight percent to about 6 weight percent rhodium, from about 0.5 wt% to about 1.5 wt% copper, from about 2 wt% to about 4 wt% nickel, from about 74 wt% to about 76 wt% indium, about 4 From wt% to about 6% by weight silver, from about 2% to about 4% by weight zinc, and from about 0.05% to about 0.2% by weight cerium, such as about 8% by weight tin, about 4.9% by weight cerium, about 1.0% by weight copper, About 3.0% by weight nickel, about 75% by weight indium, about 5% by weight silver, about 3.0% by weight zinc, and about 0.1% by weight bismuth.

在一些其他具體實例中，組成物20包括約4重量%至約20重量%錫、約0.2重量%至約8重量%銻、約0.1重量%至約4重量%銅、約 0.1重量%至約3重量%鎳、約71重量%至約86重量%銦及約1重量%至約6重量%銀。在某些具體實例中，組成物20包括約10重量%至約19重量%錫。在某些其他具體實例中，組成物20包括約74重量%至約80重量%銦。在此等特定具體實例中，組成物20可包括約1重量%至約7重量%銀。在一些具體實例中，組成物20可包括約3.5重量%銅。在某些其他具體實例中，組成物20包括約0.1重量%至約1重量%鎳。在其他具體實例中，組成物20包括約1重量%至約2重量%鎳。在其他具體實例中，組成物20包括約0.2重量%至約2重量%銻。在其他具體實例中，組成物20包括約2重量%至約6重量%銻。 In some other specific examples, composition 20 includes from about 4 wt% to about 20 wt% tin, from about 0.2 wt% to about 8 wt% bismuth, from about 0.1 wt% to about 4 wt% copper, about 0.1% by weight to about 3% by weight nickel, about 71% by weight to about 86% by weight indium, and about 1% by weight to about 6% by weight of silver. In certain embodiments, composition 20 includes from about 10% to about 19% tin by weight. In certain other specific examples, composition 20 includes from about 74% to about 80% by weight indium. In these particular embodiments, composition 20 can include from about 1% to about 7% by weight silver. In some embodiments, composition 20 can include about 3.5% copper by weight. In certain other specific examples, composition 20 includes from about 0.1% to about 1% nickel by weight. In other embodiments, composition 20 includes from about 1% to about 2% nickel by weight. In other embodiments, composition 20 includes from about 0.2% to about 2% by weight hydrazine. In other embodiments, composition 20 includes from about 2% to about 6% by weight bismuth.

在第七特定具體實例中，組成物20包括約18重量%至約20 重量%錫、約0.2重量%至約1.0重量%銻、約0.1重量%至約1.0重量%銅、約0.1重量%至約1.0重量%鎳、約77重量%至約80重量%銦及約1重量%至約3重量%銀，諸如約18.99重量%錫、約0.24重量%銻、約0.18重量%銅、約0.30重量%鎳、約78.70重量%銦及約1.48重量%銀。此特定具體實例之熔點或溫度(液相線)為約135℃且固相線為約124℃。 In a seventh specific embodiment, composition 20 comprises from about 18% to about 20% Weight % tin, from about 0.2% by weight to about 1.0% by weight bismuth, from about 0.1% by weight to about 1.0% by weight copper, from about 0.1% by weight to about 1.0% by weight nickel, from about 77% by weight to about 80% by weight indium and about 1 From % by weight to about 3% by weight silver, such as about 18.99% by weight tin, about 0.24% by weight bismuth, about 0.18% by weight copper, about 0.30% by weight nickel, about 78.70% by weight indium, and about 1.48% by weight silver. The melting point or temperature (liquidus) of this particular embodiment is about 135 ° C and the solidus line is about 124 ° C.

在第八特定具體實例中，組成物20包括約13重量%至約16 重量%錫、約1.0重量%至約3.0重量%銻、約3.0重量%至約4.0重量%銅、約0.2重量%至約1.5重量%鎳、約74重量%至約76重量%銦及約3重量%至約5重量%銀，諸如約14.77重量%錫、約1.93重量%銻、約3.50重量%銅、約0.60重量%鎳、約74.91重量%銦及約3.87重量%銀。此特定具體實例之熔點或溫度(液相線)為約135℃且固相線為約123℃。 In an eighth particular embodiment, composition 20 comprises from about 13% to about 16 Weight percent tin, from about 1.0% to about 3.0% by weight cerium, from about 3.0% to about 4.0% by weight copper, from about 0.2% to about 1.5% by weight nickel, from about 74% to about 76% by weight indium, and from about 3 From % by weight to about 5% by weight silver, such as about 14.77 weight percent tin, about 1.93 weight percent bismuth, about 3.50 weight percent copper, about 0.60 weight percent nickel, about 74.91 weight percent indium, and about 3.87 weight percent silver. The melting point or temperature (liquidus) of this particular embodiment is about 135 ° C and the solidus line is about 123 ° C.

在第九特定具體實例中，組成物20包括約11重量%至約14 重量%錫、約2.0重量%至約4重量%銻、約0.5重量%至約2重量%銅、約1.0重量%至約3重量%鎳、約76重量%至約79重量%銦及約2重量%至約5重量%銀，諸如約12.68重量%錫、約2.91重量%銻、約1.22重量%銅、約1.87重量%鎳、約77.30重量%銦及約3.54重量%銀。此特定具體實例之熔點或溫度(液相線)為約138℃且固相線為約127℃。 In a ninth specific embodiment, composition 20 comprises from about 11% to about 14% Weight % tin, from about 2.0% to about 4% by weight cerium, from about 0.5% to about 2% by weight copper, from about 1.0% to about 3% by weight nickel, from about 76% to about 79% by weight indium and about 2 From % by weight to about 5% by weight of silver, such as about 12.68% by weight tin, about 2.91% by weight bismuth, about 1.22% by weight copper, about 1.87% by weight nickel, about 77.30% by weight indium, and about 3.54% by weight silver. The melting point or temperature (liquidus) of this particular embodiment is about 138 ° C and the solidus line is about 127 ° C.

在第十特定具體實例中，組成物20包括約6重量%至約9 重量%錫、約3.0重量%至約5重量%銻、約0.5重量%至約1.5重量%銅、約1.0重量%至約3重量%鎳、約76重量%至約79重量%銦、約4重量%至約6重量%銀及約2重量%至約4重量%鋅，諸如約7.66重量%錫、約3.75重量%銻、約0.92重量%銅、約1.88重量%鎳、約77.30重量%銦、約5.21重量%銀及約3.17重量%鋅。此特定具體實例之熔點或溫度(液相線)為約143.4℃且固相線為約129℃。 In a tenth specific embodiment, the composition 20 comprises from about 6% to about 9 Weight% tin, from about 3.0% to about 5% by weight bismuth, from about 0.5% to about 1.5% by weight copper, from about 1.0% to about 3% by weight nickel, from about 76% to about 79% by weight indium, about 4 From wt% to about 6% by weight silver and from about 2% to about 4% by weight zinc, such as about 7.66 wt% tin, about 3.75 wt% bismuth, about 0.92 wt% copper, about 1.88 wt% nickel, about 77.30 wt% indium. About 5.21% by weight of silver and about 3.17% by weight of zinc. The melting point or temperature (liquidus) of this particular embodiment is about 143.4 ° C and the solidus line is about 129 ° C.

在第十一特定具體實例中，組成物20包括約7重量%至約9 重量%錫、約4重量%至約6重量%銻、約0.2重量%至約1.0重量%銅、約0.2重量%至約1.5重量%鎳、約73重量%至約76重量%銦、約4重量%至約6重量%銀及約4重量%至約6重量%鋅，諸如約8.45重量%錫、約5.42重量%銻、約0.40重量%銅、約0.54重量%鎳、約74.21重量%銦、約5.54重量%銀及約4.86重量%鋅。此特定具體實例之熔點或溫度(液相線)為約139.4℃且固相線為約127℃。 In an eleventh specific embodiment, the composition 20 comprises from about 7% by weight to about 9 Weight percent tin, from about 4 weight percent to about 6 weight percent rhodium, from about 0.2 wt% to about 1.0 wt% copper, from about 0.2 wt% to about 1.5 wt% nickel, from about 73 wt% to about 76 wt% indium, about 4 From wt% to about 6% by weight silver and from about 4% to about 6% by weight zinc, such as about 8.45 wt% tin, about 5.42 wt% bismuth, about 0.40 wt% copper, about 0.54 wt% nickel, about 74.21 wt% indium. About 5.54% by weight of silver and about 4.86% by weight of zinc. The melting point or temperature (liquidus) of this particular embodiment is about 139.4 ° C and the solidus line is about 127 ° C.

在第十二特定具體實例中，組成物20包括約4重量%至約6 重量%錫、約1.0重量%至約2.0重量%銻、約0.1重量%至約2重量%銅、約0.1重量%至約1.0重量%鎳、約84重量%至約86重量%銦、約1重量% 至約2重量%銀、約0.2重量%至約1重量%鋅及小於約0.001重量%至約0.15重量%鍺，諸如約5.31重量%錫、約1.52重量%銻、約1.07重量%銅、約0.15重量%鎳、約85.56重量%銦、約1.45重量%銀、約0.46重量%鋅及小於約0.001重量%鍺。此特定具體實例之熔點或溫度(液相線)為約140℃且固相線為約132.4℃。 In a twelfth specific embodiment, composition 20 comprises from about 4% to about 6 Weight% tin, from about 1.0% to about 2.0% by weight cerium, from about 0.1% to about 2% by weight copper, from about 0.1% to about 1.0% by weight nickel, from about 84% to about 86% by weight indium, about 1 weight% Up to about 2 weight percent silver, from about 0.2 weight percent to about 1 weight percent zinc, and less than about 0.001 weight percent to about 0.15 weight percent bismuth, such as about 5.31 weight percent tin, about 1.52 weight percent bismuth, about 1.07 weight percent copper, about 0.15 wt% nickel, about 85.56 wt% indium, about 1.45 wt% silver, about 0.46 wt% zinc, and less than about 0.001 wt% hydrazine. The melting point or temperature (liquidus) of this particular embodiment is about 140 ° C and the solidus line is about 132.4 ° C.

在第十三特定具體實例中，組成物20包括約18重量%至約 20重量%錫、約0.2重量%至約2重量%銻、約0.1重量%至約4.0重量%銅、約0.1重量%至約3.0重量%鎳、約72重量%至約75重量%銦及約1重量%至約4重量%銀，諸如約19.49重量%錫、約1.03重量%銻、約2.84重量%銅、約1.26重量%鎳、約73.62重量%銦及約2.79重量%銀。此特定具體實例之熔點或溫度(液相線)為約134.71℃且固相線為約123.74℃。 In a thirteenth specific embodiment, the composition 20 comprises from about 18% by weight to about 20% by weight tin, about 0.2% to about 2% by weight cerium, about 0.1% to about 4.0% by weight copper, about 0.1% to about 3.0% by weight nickel, about 72% to about 75% by weight indium and about 1% by weight to about 4% by weight of silver, such as about 19.49% by weight tin, about 1.03% by weight bismuth, about 2.84% by weight copper, about 1.26% by weight nickel, about 73.62% by weight indium, and about 2.79% by weight silver. The melting point or temperature (liquidus) of this particular embodiment is about 134.71 ° C and the solidus line is about 123.74 ° C.

在第十四特定具體實例中，組成物20包括約16重量%至約 19重量%錫、約3.0重量%至約6.0重量%銻、約2.0重量%至約4.0重量%銅、約0.5重量%至約3.0重量%鎳、約70重量%至約73重量%銦及約1重量%至約4重量%銀，諸如約18.23重量%錫、約4.57重量%銻、約2.7重量%銅、約1.49重量%鎳、約71.05重量%銦及約2.60重量%銀。此特定具體實例之熔點或溫度(液相線)為約135.52℃且固相線為約122.98℃。 In a fourteenth specific embodiment, the composition 20 comprises from about 16% by weight to about 19 wt% tin, from about 3.0 wt% to about 6.0 wt% bismuth, from about 2.0 wt% to about 4.0 wt% copper, from about 0.5 wt% to about 3.0 wt% nickel, from about 70 wt% to about 73 wt% indium, and about 1% by weight to about 4% by weight of silver, such as about 18.23% by weight tin, about 4.57% by weight bismuth, about 2.7% by weight copper, about 1.49% by weight nickel, about 71.05% by weight indium, and about 2.60% by weight silver. The melting point or temperature (liquidus) of this particular embodiment is about 135.52 ° C and the solidus line is about 122.98 ° C.

在第十五特定具體實例中，組成物20包括約15重量%至約 18重量%錫、約1.0重量%至約4重量%銻、約1.5重量%至約3.5重量%銅、約1.0重量%至約4重量%鎳、約71重量%至約75重量%銦及約2重量%至約5重量%銀，諸如約16.95重量%錫、約2.69重量%銻、約2.4重量%銅、約2.82重量%鎳、約72.84重量%銦及約3.31重量%銀。此特定具體實例之熔點或溫度(液相線)為約139.01℃且固相線為約125.39℃。 In a fifteenth specific embodiment, the composition 20 comprises from about 15% by weight to about 18% by weight tin, about 1.0% to about 4% by weight cerium, about 1.5% to about 3.5% by weight copper, about 1.0% to about 4% by weight nickel, about 71% to about 75% by weight indium and about 2% by weight to about 5% by weight of silver, such as about 16.95% by weight tin, about 2.69% by weight bismuth, about 2.4% by weight copper, about 2.82% by weight nickel, about 72.84% by weight indium, and about 3.31% by weight silver. Specific to this specific example The melting point or temperature (liquidus) is about 139.01 ° C and the solidus line is about 125.39 ° C.

在第十六特定具體實例中，組成物20包括約7重量%至約 11重量%錫、約3.0重量%至約5重量%銻、約1.5重量%至約3.5重量%銅、約0.5重量%至約3重量%鎳、約79重量%至約82重量%銦、約1.0重量%至約4重量%銀及約0.01重量%至約1重量%鋅，諸如約9.02重量%錫、約4.12重量%銻、約2.21重量%銅、約1.09重量%鎳、約80.12重量%銦、約2.80重量%銀及約0.05重量%鋅。此特定具體實例之熔點或溫度(液相線)為約142.11℃且固相線為約130.91℃。 In a sixteenth specific embodiment, the composition 20 comprises from about 7% by weight to about 11 wt% tin, from about 3.0 wt% to about 5 wt% bismuth, from about 1.5 wt% to about 3.5 wt% copper, from about 0.5 wt% to about 3% wt% nickel, from about 79 wt% to about 82 wt% indium, about 1.0% by weight to about 4% by weight silver and from about 0.01% by weight to about 1% by weight zinc, such as about 9.02% by weight tin, about 4.12% by weight bismuth, about 2.21% by weight copper, about 1.09% by weight nickel, about 80.12% by weight Indium, about 2.80% by weight silver, and about 0.05% by weight zinc. The melting point or temperature (liquidus) of this particular embodiment is about 142.11 ° C and the solidus line is about 130.91 ° C.

在第十七特定具體實例中，組成物20包括約9重量%至約 12重量%錫、約4重量%至約6重量%銻、約1.5重量%至約3.5重量%銅、約0.5重量%至約3.0重量%鎳、約75重量%至約78重量%銦、約1重量%至約3重量%銀及約0.01重量%至約1重量%鋅，諸如約10.69重量%錫、約5.32重量%銻、約2.58重量%銅、約1.55重量%鎳、約76.03重量%銦、約2.11重量%銀及約0.05重量%鋅。此特定具體實例之熔點或溫度(液相線)為約140.37℃且固相線為約126.93℃。 In a seventeenth specific embodiment, the composition 20 comprises from about 9% by weight to about 12% by weight tin, about 4% to about 6% by weight cerium, about 1.5% to about 3.5% by weight copper, about 0.5% to about 3.0% by weight nickel, about 75% to about 78% by weight indium, about 1% by weight to about 3% by weight of silver and about 0.01% by weight to about 1% by weight of zinc, such as about 10.69% by weight of tin, about 5.32% by weight of bismuth, about 2.58% by weight of copper, about 1.55% by weight of nickel, about 76.03% by weight Indium, about 2.11% by weight silver, and about 0.05% by weight zinc. The melting point or temperature (liquidus) of this particular embodiment is about 140.37 ° C and the solidus line is about 126.93 ° C.

在第十八特定具體實例中，組成物20包括約8重量%至約 10重量%錫、約2.0重量%至約5.0重量%銻、約2重量%至約4重量%銅、約0.5重量%至約3.0重量%鎳、約79重量%至約82重量%銦、約2重量%至約4重量%銀、約0.01重量%至約1重量%鋅及小於約0.001重量%至約0.15重量%鍺，諸如約9.03重量%錫、約3.43重量%銻、約3重量%銅、約0.95重量%鎳、約80.57重量%銦、約3.32重量%銀、約0.1重量%鋅及小於約0.001重量%鍺。此特定具體實例之熔點或溫度(液相線)為約141.67℃ 且固相線為約130.30℃。 In an eighteenth specific embodiment, the composition 20 comprises from about 8 wt% to about 10% by weight tin, about 2.0% to about 5.0% by weight cerium, about 2% to about 4% by weight copper, about 0.5% to about 3.0% by weight nickel, about 79% to about 82% by weight indium, about 2% by weight to about 4% by weight silver, about 0.01% by weight to about 1% by weight zinc and less than about 0.001% by weight to about 0.15% by weight bismuth, such as about 9.03% by weight tin, about 3.43% by weight bismuth, about 3% by weight Copper, about 0.95 weight percent nickel, about 80.57 weight percent indium, about 3.32 weight percent silver, about 0.1 weight percent zinc, and less than about 0.001 weight percent bismuth. The melting point or temperature (liquidus) of this particular embodiment is about 141.67 ° C And the solidus line is about 130.30 °C.

在第十九特定具體實例中，組成物20包括約10重量%至約 14重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約73重量%至約77重量%銦、約5重量%至約9重量%銀及約2重量%至約4重量%鋅，諸如約12重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦、約7重量%銀及約3重量%鋅。 In a nineteenth specific embodiment, the composition 20 comprises from about 10% by weight to about 14 wt% tin, from about 0.5 wt% to about 1.5 wt% bismuth, from about 0.5 wt% to about 1.5 wt% copper, from about 0.5 wt% to about 1.5 wt% nickel, from about 73 wt% to about 77 wt% indium, about 5 wt% to about 9 wt% silver and from about 2 wt% to about 4 wt% zinc, such as about 12 wt% tin, about 1 wt% bismuth, about 1 wt% copper, about 1 wt% nickel, about 75% by weight Indium, about 7% by weight silver, and about 3% by weight zinc.

在第二十特定具體實例中，組成物20包括約6重量%至約 10重量%錫、約3重量%至約7重量%銻、約0.5重量%至約1.5重量%銅、約2重量%至約4重量%鎳、約73重量%至約77重量%銦、約3重量%至約7重量%銀及約2重量%至約4重量%鋅，諸如約8重量%錫、約5重量%銻、約1重量%銅、約3重量%鎳、約75重量%銦、約5重量%銀及約3重量%鋅。 In a twentieth specific embodiment, composition 20 comprises from about 6% by weight to about 10% by weight tin, about 3% to about 7% by weight cerium, about 0.5% to about 1.5% by weight copper, about 2% to about 4% by weight nickel, about 73% to about 77% by weight indium, about 3% by weight to about 7% by weight silver and from about 2% by weight to about 4% by weight zinc, such as about 8% by weight tin, about 5% by weight bismuth, about 1% by weight copper, about 3% by weight nickel, about 75% by weight Indium, about 5% by weight silver, and about 3% by weight zinc.

在第二十一特定具體實例中，組成物20包括約12重量%至約16重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約0.5重量%至約1.5重量%鋅、約73重量%至約77重量%銦及約5重量%至約9重量%銀，諸如約14重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約1重量%鋅、約75重量%銦及約7重量%銀。 In a twenty-first specific embodiment, the composition 20 comprises about 12% by weight to About 16% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 0.5% to about 1.5% by weight zinc, From about 73% by weight to about 77% by weight indium and from about 5% by weight to about 9% by weight silver, such as about 14% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 1 weight % zinc, about 75% by weight indium, and about 7% by weight silver.

在第二十二特定具體實例中，組成物20包括約20重量%至約24重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約66重量%至約70重量%銦及約5 重量%至約9重量%銀，諸如約22重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約68重量%銦及約7重量%銀。 In a twenty-second particular embodiment, the composition 20 comprises about 20% by weight to About 24% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 66% to about 70% by weight indium, and About 5 From % by weight to about 9% by weight of silver, such as about 22% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 68% by weight indium, and about 7% by weight silver.

在第二十三特定具體實例中，組成物20包括約18重量%至約22重量%錫、約0.5重量%至約1.5重量%銻、約2重量%至約4重量%銅、約0.5重量%至約1.5重量%鎳、約66重量%至約70重量%銦及約5重量%至約9重量%銀，諸如約20重量%錫、約1重量%銻、約3重量%銅、約1重量%鎳、約68重量%銦及約7重量%銀。 In a twenty-third specific embodiment, the composition 20 comprises about 18% by weight to About 22% by weight tin, about 0.5% to about 1.5% by weight cerium, about 2% to about 4% by weight copper, about 0.5% to about 1.5% by weight nickel, about 66% to about 70% by weight indium and From about 5% by weight to about 9% by weight silver, such as about 20% by weight tin, about 1% by weight bismuth, about 3% by weight copper, about 1% by weight nickel, about 68% by weight indium, and about 7% by weight silver.

在第二十四特定具體實例中，組成物20包括約12重量%至約16重量%錫、約1重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約73重量%至約77重量%銦及約5重量%至約9重量%銀，諸如約14重量%錫、約2重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦及約7重量%銀。 In a twenty-fourth specific embodiment, the composition 20 comprises about 12% by weight to About 16% by weight tin, about 1% to about 3% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 73% to about 77% by weight indium and From about 5% by weight to about 9% by weight silver, such as about 14% by weight tin, about 2% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 75% by weight indium, and about 7% by weight silver.

在第二十五特定具體實例中，組成物20包括約11重量%至約15重量%錫、約2重量%至約4重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約73重量%至約77重量%銦及約5重量%至約9重量%銀，諸如約13重量%錫、約3重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦及約7重量%銀。 In a twenty-fifth specific embodiment, the composition 20 comprises about 11% by weight to About 15% by weight tin, about 2% to about 4% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 73% to about 77% by weight indium and From about 5% by weight to about 9% by weight silver, such as about 13% by weight tin, about 3% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 75% by weight indium, and about 7% by weight silver.

在第二十六特定具體實例中，組成物20包括約14重量%至約18重量%錫、約2重量%至約4重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約70重量%至約74重量%銦及約5重量%至約9重量%銀，諸如約16重量%錫、約3重量%銻、約1重量%銅、約1重量%鎳、約72重量%銦及約7重量%銀。 In a twenty-sixth specific embodiment, the composition 20 comprises about 14% by weight to About 18% by weight tin, about 2% to about 4% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 70% to about 74% by weight indium and From about 5% by weight to about 9% by weight silver, such as about 16% by weight tin, about 3% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 72% by weight indium, and about 7% by weight silver.

在第二十七特定具體實例中，組成物20包括約18重量%至約22重量%錫、約2重量%至約4重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約66重量%至約70重量%銦及約5重量%至約9重量%銀，諸如約20重量%錫、約3重量%銻、約1重量%銅、約1重量%鎳、約68重量%銦及約7重量%銀。 In a twenty-seventh specific embodiment, the composition 20 comprises about 18% by weight to About 22% by weight tin, about 2% to about 4% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 66% to about 70% by weight indium and From about 5% by weight to about 9% by weight silver, such as about 20% by weight tin, about 3% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 68% by weight indium, and about 7% by weight silver.

在第二十八特定具體實例中，組成物20包括約13重量%至約17重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約73重量%至約77重量%銦及約5重量%至約9重量%銀，諸如約15重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約75重量%銦及約7重量%銀。 In a twenty-eighth specific embodiment, the composition 20 comprises about 13% by weight to About 17% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 73% to about 77% by weight indium and From about 5% by weight to about 9% by weight silver, such as about 15% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 75% by weight indium, and about 7% by weight silver.

在第二十九特定具體實例中，組成物20包括約13重量%至約17重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約0.5重量%至約1.5重量%鋅、約73重量%至約77重量%銦及約5重量%至約8.5重量%銀，諸如約14.05重量%錫、約0.98重量%銻、約0.87重量%銅、約0.70重量%鎳、約0.63重量%鋅、約74.74重量%銦及約7.98重量%銀。此焊料組成物之熔點或溫度(液相線)為約133.18℃且固相線為約123.94℃。 In a twenty-ninth specific embodiment, composition 20 comprises about 13% by weight to About 17% by weight tin, about 0.5% to about 1.5% by weight cerium, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight nickel, about 0.5% to about 1.5% by weight zinc, From about 73% by weight to about 77% by weight indium and from about 5% by weight to about 8.5% by weight silver, such as about 14.05% by weight tin, about 0.98% by weight bismuth, about 0.87% by weight copper, about 0.70% by weight nickel, about 0.63 weight % zinc, about 74.74% by weight indium, and about 7.98% by weight silver. The melting point or temperature (liquidus) of this solder composition was about 133.18 ° C and the solidus line was about 123.94 ° C.

在第三十特定具體實例中，組成物20包括約12重量%至約 16重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約2重量%至約4重量%鎳、約0.5重量%至約1.5重量%鋅、約73重量%至約77重量%銦及約3重量%至約7重量%銀，諸如約14.14重量%錫、約0.76重量%銻、約0.64重量%銅、約2.24重量%鎳、約0.75重量%鋅、約 76.07重量%銦及約5.81重量%銀。此焊料組成物之熔點或溫度(液相線)為約137.58℃且固相線為約125.92℃。 In a thirtieth specific embodiment, the composition 20 comprises from about 12% by weight to about 16 wt% tin, from about 0.5 wt% to about 1.5 wt% bismuth, from about 0.5 wt% to about 1.5 wt% copper, from about 2 wt% to about 4 wt% nickel, from about 0.5 wt% to about 1.5 wt% zinc, about 73% by weight to about 77% by weight indium and about 3% to about 7% by weight silver, such as about 14.14% by weight tin, about 0.76% by weight bismuth, about 0.64% by weight copper, about 2.24% by weight nickel, about 0.75% by weight Zinc, about 76.07 wt% indium and about 5.81 wt% silver. The melting point or temperature (liquidus) of this solder composition was about 137.58 ° C and the solidus line was about 125.92 ° C.

在第三十一特定具體實例中，組成物20包括約11重量%至約15重量%錫、約1重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約3重量%至約5重量%鎳、約0.3重量%至約1.5重量%鋅、約72重量%至約76重量%銦及約4重量%至約6重量%銀，諸如約13.43重量%錫、約1.31重量%銻、約0.94重量%銅、約2.65重量%鎳、約0.49重量%鋅、約72.97重量%銦及約7.54重量%銀。此焊料組成物之熔點或溫度(液相線)為約140.64℃且固相線為約129.24℃。 In a thirty-first specific embodiment, the composition 20 comprises about 11% by weight to About 15% by weight tin, about 1% to about 3% by weight cerium, about 0.5% to about 1.5% by weight copper, about 3% to about 5% by weight nickel, about 0.3% to about 1.5% by weight zinc, From about 72% by weight to about 76% by weight indium and from about 4% by weight to about 6% by weight silver, such as about 13.43% by weight tin, about 1.31% by weight bismuth, about 0.94% by weight copper, about 2.65% by weight nickel, about 0.49 weight % zinc, about 72.97 wt% indium, and about 7.54 wt% silver. The melting point or temperature (liquidus) of this solder composition was about 140.64 ° C and the solidus line was about 129.24 ° C.

在第三十二特定具體實例中，組成物20基本上由以下組成：約13重量%至約17重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鎳、約0.5重量%至約1.5重量%鋅、約73重量%至約77重量%銦及約5重量%至約8.5重量%銀，諸如約14.05重量%錫、約0.98重量%銻、約0.87重量%銅、約0.70重量%鎳、約0.63重量%鋅、約74.74重量%銦及約7.98重量%銀。此焊料組成物之熔點或溫度(液相線)為約133.18℃且固相線為約123.94℃。此焊料組成物之電阻率為約16.24×10^-6Ω．cm。 In a thirty-second specific embodiment, composition 20 consists essentially of from about 13% to about 17% tin, from about 0.5% to about 1.5% by weight, from about 0.5% to about 1.5% by weight. Copper, from about 0.5% to about 1.5% by weight nickel, from about 0.5% to about 1.5% by weight zinc, from about 73% to about 77% by weight indium, and from about 5% to about 8.5 % by weight silver, such as about 14.05 weight % tin, about 0.98 wt% bismuth, about 0.87 wt% copper, about 0.70 wt% nickel, about 0.63 wt% zinc, about 74.74 wt% indium, and about 7.98 wt% silver. The melting point or temperature (liquidus) of this solder composition was about 133.18 ° C and the solidus line was about 123.94 ° C. The solder composition has a resistivity of about 16.24 x 10 ^-6 Ω. Cm.

如在本申請案中所用，在一些具體實例中，基本上由所列材料組成之焊料組成物限於規定材料及並不實質上影響焊料組成物及包括焊料組成物之電連接器的基本及新穎特性的材料。焊料組成物之基本及新穎特性包括本文所述之熱性質(例如液相線及固相線溫度)及機械性質(例如下文所述之性能測試)。 As used in this application, in some embodiments, substantially by listing The solder composition of the composition is limited to the specified materials and materials that do not substantially affect the basic and novel properties of the solder composition and electrical connectors including the solder composition. The basic and novel properties of the solder composition include the thermal properties (e.g., liquidus and solidus temperature) and mechanical properties (e.g., performance tests described below) as described herein.

在第三十三特定具體實例中，組成物20基本上由以下組成：約12重量%至約16重量%錫、約0.5重量%至約1.5重量%銻、約0.5重量%至約1.5重量%銅、約2重量%至約4重量%鎳、約0.5重量%至約1.5重量%鋅、約73重量%至約77重量%銦及約3重量%至約7重量%銀，諸如約14.14重量%錫、約0.76重量%銻、約0.64重量%銅、約2.24重量%鎳、約0.75重量%鋅、約76.07重量%銦及約5.81重量%銀。此焊料組成物之熔點或溫度(液相線)為約137.58℃且固相線為約125.92℃。 In a thirty-third specific embodiment, the composition 20 consists essentially of the following group Form: from about 12% by weight to about 16% by weight tin, from about 0.5% by weight to about 1.5% by weight bismuth, from about 0.5% by weight to about 1.5% by weight copper, from about 2% by weight to about 4% by weight nickel, about 0.5% by weight Up to about 1.5% by weight zinc, about 73% to about 77% by weight indium, and about 3% to about 7% by weight silver, such as about 14.14% by weight tin, about 0.76% by weight bismuth, about 0.64% by weight copper, about 2.24 Weight% nickel, about 0.75% by weight zinc, about 76.07% by weight indium, and about 5.81% by weight silver. The melting point or temperature (liquidus) of this solder composition was about 137.58 ° C and the solidus line was about 125.92 ° C.

在第三十四特定具體實例中，組成物20基本上由以下組成：約11重量%至約15重量%錫、約1重量%至約3重量%銻、約0.5重量%至約1.5重量%銅、約3重量%至約5重量%鎳、約0.3重量%至約1.5重量%鋅、約72重量%至約76重量%銦及約4重量%至約8重量%銀，諸如約13.43重量%錫、約1.31重量%銻、約0.94重量%銅、約2.65重量%鎳、約0.49重量%鋅、約72.97重量%銦及約7.54重量%銀。此焊料組成物之熔點或溫度(液相線)為約140.64℃且固相線為約129.24℃。 In a thirty-fourth specific embodiment, the composition 20 consists essentially of the following group Form: from about 11% by weight to about 15% by weight tin, from about 1% by weight to about 3% by weight bismuth, from about 0.5% by weight to about 1.5% by weight copper, from about 3% by weight to about 5% by weight nickel, about 0.3% by weight To about 1.5% by weight zinc, about 72% to about 76% by weight indium, and about 4% to about 8% by weight silver, such as about 13.43% by weight tin, about 1.31% by weight bismuth, about 0.94% by weight copper, about 2.65 Weight percent nickel, about 0.49 weight percent zinc, about 72.97 weight percent indium, and about 7.54 weight percent silver. The melting point or temperature (liquidus) of this solder composition was about 140.64 ° C and the solidus line was about 129.24 ° C.

其他組成物可包括約8重量%錫、約10重量%銻、約1重量 %銅、約1重量%鎳、約75重量%銦及約5重量%銀；或約11重量%錫、約10重量%銻、約1重量%銅、約1重量%鎳、約72重量%銦及約5重量%銀；或約14重量%錫、約1重量%銻、約1重量%銅、約1重量%鎳、約1重量%鍺、約75重量%銦及約7重量%銀；或約21重量%錫、約1重量%銻、約1重量%銅、約68重量%銦及約9重量%銀；或約22重量%錫、約1重量%銻、約5重量%銅、約1重量%鎳、約68重量%銦及約7重量%銀；或約16重量%錫、約1重量%銻、約5重量%銅、約1重量%鎳、約68重量%銦及約9重量%銀；或約17重量%錫、約1重量%銻、約5重量%銅、約68重量%銦及約9重量%銀；或約16重量%錫、約3重量%銻、約1重量%銅、約75重量%銦及約5重量%銀。 Other compositions may include about 8% by weight tin, about 10% by weight bismuth, about 1 weight % copper, about 1% by weight nickel, about 75% by weight indium, and about 5% by weight silver; or about 11% by weight tin, about 10% by weight bismuth, about 1% by weight copper, about 1% by weight nickel, about 72% by weight Indium and about 5% by weight silver; or about 14% by weight tin, about 1% by weight cerium, about 1% by weight copper, about 1% by weight nickel, about 1% by weight cerium, about 75% by weight indium, and about 7% by weight silver Or about 21% by weight tin, about 1% by weight bismuth, about 1% by weight copper, about 68% by weight indium, and about 9% by weight silver; or about 22% by weight tin, about 1% by weight bismuth, about 5% by weight copper About 1% by weight of nickel, about 68% by weight of indium, and about 7% by weight of silver; or about 16% by weight of tin, about 1% by weight of cerium, about 5% by weight of copper, about 1% by weight of nickel, about 68% by weight of indium and About 9% by weight of silver; or about 17% by weight tin, about 1% by weight bismuth, about 5% by weight copper, about 68% by weight indium, and about 9% by weight silver; or about 16% by weight tin, about 3% by weight bismuth, About 1% by weight copper, about 75% by weight indium, and about 5% by weight silver.

本發明亦係關於如圖1及圖2中所示之玻璃組件上的電連接，其包括玻璃組件、玻璃組件上含有銀之電接點表面及用焊料組成物層焊接至玻璃組件上之電接點表面上的電連接器，該焊料組成物具有包含約4重量%至約25重量%錫、約0.1重量%至約8重量%銻、約0.03重量%至約4重量%銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀的元素混合物。在其他具體實例中，玻璃組件上之電連接包括玻璃組件、玻璃組件上含有銀之電接點表面及用焊料組成物層焊接至玻璃組件上之電接點表面上的電連接器，該焊料組成物基本上由以下組成：約4重量%至約25重量%錫、約0.1重量%至約8重量%銻、約0.03重量%至約4重量%銅、約0.03重量%至約4重量%鎳、約66重量%至約90重量%銦及約0.5重量%至約9重量%銀。 The invention is also related to the electrical connection on the glass component as shown in Figures 1 and 2 Connected, comprising a glass component, an electrical contact surface comprising silver on the glass component, and an electrical connector soldered to the surface of the electrical contact on the glass component with a solder composition layer, the solder composition having about 4% by weight to About 25 wt% tin, about 0.1 wt% to about 8 wt% bismuth, about 0.03 wt% to about 4 wt% copper, about 0.03 wt% to about 4 wt% nickel, about 66 wt% to about 90 wt% indium, and A mixture of elements of from about 0.5% by weight to about 9% by weight silver. In other embodiments, the electrical connection on the glass component includes a glass component, an electrical contact surface comprising silver on the glass component, and an electrical connector soldered to the surface of the electrical contact on the glass component with a solder composition layer, the solder The composition consists essentially of from about 4% to about 25% by weight tin, from about 0.1% to about 8% by weight cerium, from about 0.03% to about 4% by weight copper, from about 0.03% to about 4% by weight. Nickel, from about 66% by weight to about 90% by weight indium and from about 0.5% by weight to about 9% by weight of silver.

圖3A中所示形成焊料組成物20之方法100包括將銦、鎳、銅、銀、銻及錫混合在一起形成包括約66重量%至約90重量%銦、約0.5重量%至約9重量%銀、約0.03重量%至約3重量%鎳、約0.03重量%至約4重量%銅、約0.1重量%至約8重量%銻及約4重量%至約25重量%錫的合金。方法100包括在步驟110熔融銦及錫及在步驟120添加銻。方法100可視情況包括在步驟130混合約0.3重量%至約5重量%鋅及在步驟140視情況混合約0.01重量%至約0.3重量%鍺。在一些具體實例中，銦與錫在步驟110一起混合於第一熔融混合物中，且至少鎳、銅及銀在步驟115於溶液中一起混合於第二混合物中，隨後在步驟125冷卻其，視情況在步驟135進行粉碎，且隨後在步驟150添加至第一熔融混合物中。形成焊料組成物20之方法的流程圖顯示於圖3A中。方法可在環境空氣氛圍中進行，無需惰性氣體環境或真空。 The method 100 of forming the solder composition 20 shown in FIG. 3A includes indium, nickel, The copper, silver, antimony and tin are mixed together to form from about 66% to about 90% by weight indium, from about 0.5% to about 9% by weight silver, from about 0.03% to about 3% by weight nickel, from about 0.03% by weight to An alloy of about 4% by weight copper, from about 0.1% to about 8% by weight bismuth and from about 4% to about 25% by weight tin. The method 100 includes melting indium and tin in step 110 and adding germanium in step 120. The method 100 can optionally include mixing about 0.3% to about 5% by weight zinc in step 130 and mixing from about 0.01% to about 0.3% by weight hydrazine as appropriate in step 140. In some embodiments, indium and tin are mixed together in the first molten mixture in step 110, and at least nickel, copper, and silver are in solution at step 115. Mixing together in the second mixture, followed by cooling it at step 125, optionally pulverizing at step 135, and then adding to the first molten mixture at step 150. A flow chart of a method of forming solder composition 20 is shown in Figure 3A. The method can be carried out in an ambient air atmosphere without the need for an inert gas atmosphere or vacuum.

在一些具體實例中，銦以約70重量%至約80重量%之比例混合、銀以約4重量%至約8重量%之比例混合、鎳以約0.1重量%至約4重量%之比例混合、銅以約0.1重量%至約1.5重量%之比例混合、銻以約0.2重量%至約8重量%之比例混合且錫以約7重量%至約19重量%之比例混合。所得合金具有呈以上針對焊料組成物20所述之比例的銦、銀、鎳、銅、銻、錫及視情況選用之鋅及鍺。 In some embodiments, indium is present in a ratio of from about 70% to about 80% by weight. Mixing, silver is mixed in a ratio of about 4% by weight to about 8% by weight, nickel is mixed in a ratio of about 0.1% by weight to about 4% by weight, copper is mixed in a ratio of about 0.1% by weight to about 1.5% by weight, and about The mixture is mixed in a ratio of 0.2% by weight to about 8% by weight and tin is mixed in a ratio of about 7% by weight to about 19% by weight. The resulting alloy has indium, silver, nickel, copper, bismuth, tin, and optionally zinc and antimony in the proportions described above for solder composition 20.

在其他具體實例中，形成焊料組成物20之方法100包括將銦、鎳、銅、鋅、銀、銻及錫混合在一起形成包括約72重量%至約77重量%銦、約4重量%至約8.5重量%銀、約0.5重量%至約5重量%鎳、約0.5重量%至約1.5重量%銅、約0.3重量%至約1.5重量%鋅、約0.5重量%至約3重量%銻及約11重量%至約17重量%錫的合金。在此等特定具體實例中，組成物20可包括約74重量%至約75重量%銦、約5重量%至約6重量%銀、約1重量%至約4重量%鎳、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鋅、約0.5重量%至約2.5重量%銻及約13重量%至約15重量%錫。此等特定具體實例之實例可包括約75重量%銦、約6重量%銀、約1重量%鎳、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鋅、約0.5重量%至約1.5重量%銻及約15重量%錫，諸如約75重量%銦、約6重量%銀、約1重量%鎳、約1重量%銅、約1重量%鋅、約1重量%銻及約 15重量%錫。此等特定具體實例之其他實例可包括約75重量%銦、約5重量%銀、約3重量%鎳、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鋅、約0.5重量%至約1.5重量%銻及約14重量%錫，諸如約75重量%銦、約5重量%銀、約3重量%鎳、約1重量%銅、約1重量%鋅、約1重量%銻及約14重量%錫。此等特定具體實例之其他實例可包括約74重量%銦、約5重量%銀、約4重量%鎳、約0.5重量%至約1.5重量%銅、約0.5重量%至約1.5重量%鋅、約1.5重量%至約2.5重量%銻及約13重量%錫，諸如約74重量%銦、約5重量%銀、約4重量%鎳、約1重量%銅、約1重量%鋅、約2重量%銻及約13重量%錫。 In other specific examples, the method 100 of forming the solder composition 20 includes Indium, nickel, copper, zinc, silver, antimony and tin are mixed together to form from about 72% to about 77% by weight indium, from about 4% to about 8.5% by weight silver, from about 0.5% to about 5% by weight nickel. An alloy of from about 0.5% by weight to about 1.5% by weight copper, from about 0.3% to about 1.5% by weight zinc, from about 0.5% to about 3% by weight bismuth and from about 11% to about 17% by weight tin. In these particular embodiments, composition 20 can include from about 74% to about 75% by weight indium, from about 5% to about 6% by weight silver, from about 1% to about 4% by weight nickel, about 0.5% by weight. To about 1.5% by weight copper, from about 0.5% to about 1.5% by weight zinc, from about 0.5% to about 2.5% by weight bismuth and from about 13% to about 15% by weight tin. Examples of such specific embodiments may include about 75% by weight indium, about 6% by weight silver, about 1% by weight nickel, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight zinc, about 0.5% by weight to about 1.5% by weight bismuth and about 15% by weight tin, such as about 75% by weight indium, about 6% by weight silver, about 1% by weight nickel, about 1% by weight copper, about 1% by weight zinc, about 1 weight %锑和约 15% by weight tin. Other examples of such specific embodiments can include about 75% by weight indium, about 5% by weight silver, about 3% by weight nickel, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight zinc, From about 0.5% by weight to about 1.5% by weight cerium and about 14% by weight tin, such as about 75% by weight indium, about 5% by weight silver, about 3% by weight nickel, about 1% by weight copper, about 1% by weight zinc, about 1 Weight % 锑 and about 14% by weight tin. Other examples of such specific embodiments may include about 74% by weight indium, about 5% by weight silver, about 4% by weight nickel, about 0.5% to about 1.5% by weight copper, about 0.5% to about 1.5% by weight zinc, From about 1.5% by weight to about 2.5% by weight bismuth and about 13% by weight tin, such as about 74% by weight indium, about 5% by weight silver, about 4% by weight nickel, about 1% by weight copper, about 1% by weight zinc, about 2 Weight% 锑 and about 13% by weight tin.

圖3B中所示之形成上述焊料組成物20之另一方法200包括在步驟210在高溫熔爐鍋(諸如感應加熱熔錫鍋(例如S.M.Manfredy，型號N.481))中加熱所需量之錫(Sn)直至錫完全熔融。感應加熱熔錫鍋為適宜用於將相對較小批量焊料加熱至高溫的熔爐，但其需要隨後進行在鍋中添加成分並攪拌熔融混合物，同時出於安全原因關掉電流(加熱)。在步驟220，關掉鍋且所需量之鎳(Ni)以較佳3/16"見方厚度約0.010"之薄片形式添加。下文所述之所有其他金屬均可以鑄錠形式添加。觀察到，在攪拌下，鎳薄片黏附於熔融混合物上且相較於鎳粉更易於熔融成溶液，且將鎳熔融成溶液相對困難之部分原因在於鎳為此焊料組成物中熔點最高的金屬(熔點1455℃)。在攪拌之後，鎳在步驟230成為溶液，打開鍋至高熱持續約10分鐘，直至熔融溫度達到約1500℉。隨後，在步驟240，再次關掉鍋且添加所需量之銅(Cu)、銀(Ag)、銦(In)、銻(Sb)及視情況選用之鍺(Ge)且在步驟250攪拌，直至其熔融成金屬溶液。隨後，在步驟255打開鍋至高熱，直至熔融溫度達到約1400℉。在步驟260關掉鍋，且添加所需(視情況選用之)量之鋅(Zn)且攪拌直至熔融成金屬溶液。隨後打開鍋至低熱持續幾分鐘以平衡金屬溶液，此後合金備用於傾注成鑄錠。觀察到鋅需要作為最後成分添加，原因在於其熔點相對較低(熔點419.5℃)且含鋅金屬溶液過度的曝露於高溫可導致鋅自金屬溶液中汽化。 Another method 200 of forming the solder composition 20 shown in FIG. 3B includes The desired amount of tin (Sn) is heated in a high temperature furnace pot (such as an induction heating pot (e.g., S.M. Manfredy, model number N.481)) in step 210 until the tin is completely melted. Induction heating tin pots are furnaces suitable for heating relatively small batches of solder to high temperatures, but which require subsequent addition of ingredients to the pot and agitation of the molten mixture while turning off the current (heating) for safety reasons. At step 220, the pan is turned off and the desired amount of nickel (Ni) is added in the form of a sheet having a preferred 3/16" square thickness of about 0.010". All other metals described below can be added in the form of ingots. It was observed that under stirring, the nickel flakes adhered to the molten mixture and were more easily melted into a solution than the nickel powder, and the reason why it was relatively difficult to melt the nickel into a solution was that nickel was the metal having the highest melting point in the solder composition ( Melting point 1455 ° C). After stirring, the nickel becomes a solution in step 230, and the pot is opened to high heat for about 10 minutes until the melting temperature reaches about 1500 °F. Subsequently, in step 240, the pot is turned off again and the required amount of copper (Cu), silver (Ag), indium (In), antimony (Sb) and, optionally, germanium (Ge) are added and stirred at step 250, Until it melts into a metal solution. Then, at step 255 Turn the pot to high heat until the melting temperature reaches about 1400 °F. The pot is turned off at step 260 and the desired (as appropriate) amount of zinc (Zn) is added and stirred until molten into a metal solution. The pan is then opened to low heat for a few minutes to equilibrate the metal solution, after which the alloy is ready for pouring into an ingot. It was observed that zinc needs to be added as a final component because its melting point is relatively low (melting point 419.5 ° C) and excessive exposure of the zinc-containing metal solution to high temperatures can cause zinc to vaporize from the metal solution.

元素在焊料組成物中之作用 The role of elements in solder composition

本發明之焊料組成物為一種無鉛合金，其提供較高操作溫度以及在強度及延性方面之機械性質及本發明應用中所需之在潤濕及穩定性方面的物理性質，同時提供所需可製造性。所需可製造性包括能夠實現足夠低之製程溫度，使得常在焊接含銀金屬化電接點表面時發生的製造易出現缺陷或故障及銀浸出(除去)現象減少或消除。此係藉由用銻、銅、鎳、銀、錫及視情況選用之鍺及鋅冶金合金化或沈澱或分散之銦基材料來實現。 The solder composition of the present invention is a lead-free alloy that provides higher operating temperatures and mechanical properties in terms of strength and ductility as well as physical properties in terms of wetting and stability required in the application of the present invention, while providing the desired Manufacturability. The manufacturability required includes the ability to achieve sufficiently low process temperatures such that manufacturing defects or failures and silver leaching (removal) phenomena that occur when soldering silver-containing metallized electrical contact surfaces are often reduced or eliminated. This is achieved by using bismuth, copper, nickel, silver, tin, and optionally zinc and metallurgical alloying or precipitation or dispersion of indium-based materials.

鎳及銅與其他元素組合有助於總體性能(包括所需之處理溫度升高)且亦有助於在指定製程條件下的機械性質。鎳及銅即使以少量(諸如0.03重量%)添加亦可有效。此等量比一般公認之鎳雜質含量(0.01%)大且比並不包括用銅電路焊接至印刷電路板上之應用中一般公認之銅雜質含量大。銻與其他元素組合有助於獲得所要溫度範圍。銻即使以少量(諸如0.1重量%)添加亦可有效。鋅與其他元素組合有助於增強合金強度而不實質上降低處理溫度。鋅即使以少量(諸如0.3重量%)添加亦可有效，其比一般公認之鋅雜質含量(0.003%)大。鍺與其他元素組合可有助於焊料組成物之可處理性，此歸因於其抗氧化性，但在一些情況下鍺在組成物中可能不易偵測到。鍺即使以少量(諸如0.01重量%或更低)添加亦可有效。 The combination of nickel and copper with other elements contributes to overall performance (including the required increase in processing temperature) and also contributes to mechanical properties under specified process conditions. Nickel and copper can be effectively added even in a small amount (such as 0.03% by weight). These amounts are greater than the generally accepted nickel impurity content (0.01%) and are generally greater than the generally accepted copper impurity content in applications that do not include soldering to printed circuit boards with copper circuitry. The combination of 锑 and other elements helps to achieve the desired temperature range. It is effective even if it is added in a small amount (such as 0.1% by weight). The combination of zinc with other elements helps to enhance the strength of the alloy without substantially reducing the processing temperature. Zinc can be effectively added even in a small amount (such as 0.3% by weight), which is larger than the generally recognized zinc impurity content (0.003%). The combination of cerium with other elements can contribute to the handleability of the solder composition due to its oxidation resistance, but in some cases bismuth may not be readily detectable in the composition. It is effective even if it is added in a small amount (such as 0.01% by weight or less).

例證 illustration

焊料組成物20之重量%結果之特定實施例係利用感應耦合電漿原子發射光譜(ICP-AEC)獲得。固相線及液相線溫度結果係利用差示掃描熱量測定法(DSC)獲得。 A specific example of the weight % of solder composition 20 results from inductively coupled plasma atomic emission spectroscopy (ICP-AEC). Solid-phase and liquidus temperature results were obtained by differential scanning calorimetry (DSC).

焊料性能測試及結果 Solder performance test and results

I.溫度循環測試 I. Temperature cycle test

此測試根據DIN EN ISO 16750-4-H章節5.3.1.2進行。測試樣品為其中電力連接器用本發明之焊料組成物之特定具體實例焊接的11塊玻璃前窗(4塊較大、4塊中等及3塊較小)。各自之凸起的狹長橋連部分在相對末端上兩個以一定距離間隔之焊料墊19之間延伸的橋連端點電力連接器18a及18b的示意圖分別顯示於圖4A及圖4B中。電力連接器18a及18b在下文中稱作電力連接器18；各焊料墊19之面積為約64mm²，且如圖5中所示，焊料組成物20具有約0.5mm之厚度。電力連接器18藉由以下操作焊接於前窗10上：將焊料鑄錠輥壓成焊料帶，在銅基材料上將焊料帶回焊成連續條，將焊料條削成均勻尺寸，使用標準工具衝壓並使端點(terminal)成形，塗覆助熔劑於焊料表面上，且使用電阻焊接元件以範圍在約750瓦特．秒至約1050瓦特．秒內(諸如約900瓦特．秒)的能量輸入將電力連接器18焊接至前窗10上的電接點條16之目標區域，隨後冷卻，同時將電力連接器18固定就位於前窗10上並持續範圍在約8秒至約12秒內(諸如約10秒)的時間。焊料組成物20基本上由以下組成：約14.05重量%錫、約0.98重量%銻、約0.87重量%銅、約0.70重量%鎳、約0.63重量%鋅、約74.74重量%銦及約7.98重量%銀。此焊料組成物之熔點或溫度(液相線) 為約133.18℃且固相線為約123.94℃。包括與電接點條16及前窗10上之電力線22連接之電力連接器18的完成之總成的示意圖顯示於圖6中。 This test is carried out in accordance with DIN EN ISO 16750-4-H section 5.3.1.2. The test samples were 11 glass front windows (4 large, 4 medium and 3 small) in which the power connector was soldered with a specific embodiment of the solder composition of the present invention. Schematic diagrams of the bridging terminal power connectors 18a and 18b extending between the two spaced apart solder pads 19 at opposite ends of the respective raised elongated bridge portions are shown in Figures 4A and 4B, respectively. The power connectors 18a and 18b are hereinafter referred to as power connectors 18; the area of each solder pad 19 is about 64 mm ² , and as shown in FIG. 5, the solder composition 20 has a thickness of about 0.5 mm. The power connector 18 is soldered to the front window 10 by pressing a solder ingot into a solder strip, stripping the solder back to a continuous strip on the copper-based material, and cutting the solder strip into a uniform size using standard tools Stamping and shaping the terminal, applying a flux to the solder surface, and using a resistance welding element to range from about 750 watts. Seconds to about 1050 watts. An energy input in seconds (such as about 900 watts per second) welds the power connector 18 to the target area of the electrical contact strip 16 on the front window 10, and then cools while the power connector 18 is secured to the front window 10. And for a time ranging from about 8 seconds to about 12 seconds, such as about 10 seconds. The solder composition 20 consists essentially of: about 14.05 wt% tin, about 0.98 wt% bismuth, about 0.87 wt% copper, about 0.70 wt% nickel, about 0.63 wt% zinc, about 74.74 wt% indium, and about 7.98 wt%. silver. The melting point or temperature (liquidus) of this solder composition was about 133.18 ° C and the solidus line was about 123.94 ° C. A schematic diagram of a completed assembly including a power connector 18 coupled to the electrical contact strip 16 and the power line 22 on the front window 10 is shown in FIG.

在此測試中(說明於圖7中)，氣候控制室(例如Russells, Holland MI，型號RDV-42-25-25/11900955在相對乾燥濕度下，但不受控制)之溫度在8小時總時間期間自環境(約20℃)至-40℃循環且保持在-40℃下90分鐘，隨後緩升至105℃並持續120分鐘，隨後重回至環境溫度，同時自-40℃步驟結束時開始經由電力線22施加14V電流負載且終止於105℃步驟結束時，如圖7中所示各別箭頭所指示。在20個循環之後，如圖8中所示，在拉力測試300中(在環境溫度下)以整體垂直於焊料層20及前窗表面10之方向將各電力連接器18在數位測力計310(Mark-10 Long Island,NY，型號BG100)上牽拉至50N之力並持續3秒，該數位測力計310利用鉤320與電力連接器18在大致於焊料墊19之間的中點處連接，且利用手柄330人工操作。在此測試期間未發生故障(亦即連接器斷開)。 In this test (described in Figure 7), the climate control room (eg Russells, Holland MI, model RDV-42-25-25/11900955 at relatively dry humidity, but uncontrolled) The temperature is cycled from ambient (about 20 ° C) to -40 ° C during the total time of 8 hours and maintained at -40 ° C The next 90 minutes, then ramp up to 105 ° C for 120 minutes, then return to ambient temperature, while applying a 14V current load via power line 22 from the end of the -40 ° C step and ending at 105 ° C at the end of the step, as shown in Figure 7. Indicated by the respective arrows shown in . After 20 cycles, as shown in FIG. 8, each power connector 18 is in the digital load cell 310 in a tensile test 300 (at ambient temperature) in a direction that is generally perpendicular to the solder layer 20 and the front window surface 10. (Mark-10 Long Island, NY, model BG100) is pulled to a force of 50 N for 3 seconds, the digital load cell 310 utilizing the hook 320 and the power connector 18 at a midpoint between the solder pads 19 Connected and manually operated using handle 330. No faults occurred during this test (ie, the connector was disconnected).

II.熱浸測試(Heat Soak Test) II. Hot Soak Test

此測試根據DIN EN ISO 16750-4-K章節5.1.2.2在9個前窗樣品上進行，該等前窗樣品包括5個用測試I中所用相同的焊料組成物焊接的電力連接器。兩個前窗樣品使用基本上由以下組成之焊料組成物：約14.14重量%錫、約0.76重量%銻、約0.64重量%銅、約2.24重量%鎳、約0.75重量%鋅、約76.07重量%銦及約5.81重量%銀。此焊料組成物之熔點或溫度(液相線)為約137.58℃且固相線為約125.92℃。另外兩個前窗樣品使用基本上由以下組成之焊料組成物：約13.43重量%錫、約1.31重量%銻、約0.94重量%銅、約2.65重量%鎳、約0.49重量%鋅、約72.97重量%銦及約7.54 重量%銀。此焊料組成物之熔點或溫度(液相線)為約140.64℃且固相線為約129.24℃。 This test was carried out on nine front window samples according to DIN EN ISO 16750-4-K section 5.1.2.2, which included five power connectors soldered with the same solder composition used in Test I. The two front window samples used a solder composition consisting essentially of: about 14.14 wt% tin, about 0.76 wt% bismuth, about 0.64 wt% copper, about 2.24 wt% nickel, about 0.75 wt% zinc, about 76.07 wt%. Indium and about 5.81% by weight of silver. The melting point or temperature (liquidus) of this solder composition was about 137.58 ° C and the solidus line was about 125.92 ° C. The other two front window samples used a solder composition consisting essentially of: about 13.43 wt% tin, about 1.31 wt% rhodium, about 0.94 wt% copper, about 2.65 wt% nickel, about 0.49 wt% zinc, about 72.97 wt. % indium and about 7.54 Weight% silver. The melting point or temperature (liquidus) of this solder composition was about 140.64 ° C and the solidus line was about 129.24 ° C.

在此測試400中(說明於圖9中)，氣候控制室(A & W Blake Hot Chamber)之溫度在105℃下保持96小時，同時在整個96小時期間經由電力線22施加14V之電流負載及以整體垂直於焊料層20及前窗表面10之方向施加6N由於重力加速度而垂直向下定向的機械負載(利用位於大致在焊料墊19之間中點處之經鉤420與電力連接器18連接的砝碼410施加)。電力連接器之溫度(利用熱電偶430量測)在測試期間因所施加之電負載而增至約120℃之最大值。在96小時測試之後，如圖8中所示且如上所述(在環境溫度下)在數位測力計(Mark-10 Long Island，型號BG50)上將各電力連接器牽拉至50N之力並持續3秒。在此測試期間未發生故障(亦即連接器斷開或微裂隙)。 In this test 400 (described in Figure 9), Climate Control Room (A & W Blake) The temperature of the Hot Chamber) was maintained at 105 ° C for 96 hours while applying a current load of 14 V via the power line 22 throughout the 96 hours and applying 6 N in a direction perpendicular to the solder layer 20 and the front window surface 10 as a whole. The underlying mechanical load (applied by a weight 410 located at a midpoint between the solder pads 19 at the midpoint between the solder pads 19 and the power connector 18). The temperature of the power connector (measured by thermocouple 430) increased to a maximum of about 120 °C during the test due to the applied electrical load. After the 96 hour test, each power connector was pulled to a force of 50 N on a digital dynamometer (Mark-10 Long Island, model BG50) as shown in Figure 8 and as described above (at ambient temperature) Lasts 3 seconds. No faults occurred during this test (ie, connector breaks or micro-cracks).

III.高溫儲存測試 III. High temperature storage test

此測試在與以上針對測試I所用之相同測試樣品上進行。在此測試中，氣候控制室(在相對乾燥濕度下，但不受控制)之溫度維持在恆定120℃下並持續24小時，同時電力連接器無電負載或機械負載。在24小時結束之後，如圖8中所示且如上所述(在環境溫度下)在數位測力計(Mark-10 Long Island,NY，型號BG100)上將各電力連接器牽拉至50N之力並持續3秒。在此測試期間未發生故障(亦即連接器斷開)。 This test was performed on the same test sample as used above for Test I. In this test, the temperature of the climate control chamber (under relatively dry humidity, but uncontrolled) was maintained at a constant 120 ° C for 24 hours while the power connector had no electrical or mechanical load. After the end of 24 hours, each power connector was pulled to 50N on a digital dynamometer (Mark-10 Long Island, NY, model BG100) as shown in Figure 8 and as described above (at ambient temperature) Force for 3 seconds. No faults occurred during this test (ie, the connector was disconnected).

IV.長期電負載測試 IV. Long-term electric load test

此測試在與以上針對測試I及測試III所用之相同測試樣品上進行。在此測試中，氣候控制室(濕度相對乾燥，但不受控制)之溫度維持在恆定105℃下並持續500小時，且在整個500小時期間電流負載為14V。在500小時結束之後，如圖8中所示且如上所述(在環境溫度下)在數位測力計(Mark-10 Long Island,NY，型號BG100)上將各電力連接器牽拉至50N之力並持續3秒。在此測試期間未發生故障(亦即連接器斷開)。 This test was performed on the same test samples as used above for Test I and Test III. In this test, the temperature of the climate control room (relatively dry but uncontrolled) It was maintained at a constant 105 ° C for 500 hours and the current load was 14 V throughout the 500 hour period. After the end of 500 hours, each power connector was pulled to 50N on a digital dynamometer (Mark-10 Long Island, NY, model BG100) as shown in Figure 8 and as described above (at ambient temperature) Force for 3 seconds. No faults occurred during this test (ie, the connector was disconnected).

V.熱驟變測試 V. Thermal shock test

此測試根據DIN EN ISO 16750-4-H章節5.4.2進行。測試樣品為5個各具有30個電力連接器之12"×12"強化玻璃板。板為4mm厚，經染色，以搪瓷印刷且套印有6個1"寬之銀條。電力連接器焊接於銀條上。兩個板上之電力連接器用基本上由以下組成之焊料組成物焊接：約14.05重量%錫、約0.98重量%銻、約0.87重量%銅、約0.70重量%鎳、約0.63重量%鋅、約74.74重量%銦及約7.98重量%銀。此焊料組成物之熔點或溫度(液相線)為約133.18℃且固相線為約123.94℃。另一板上之電力連接器用基本上由以下組成之焊料組成物焊接：約14.14重量%錫、約0.76重量%銻、約0.64重量%銅、約2.24重量%鎳、約0.75重量%鋅、約76.07重量%銦及約5.81重量%銀。此焊料組成物之熔點或溫度(液相線)為約137.58℃且固相線為約125.92℃。另一板上之電力連接器用基本上由以下組成之焊料組成物焊接：約13.43重量%錫、約1.31重量%銻、約0.94重量%銅、約2.65重量%鎳、約0.49重量%鋅、約72.97重量%銦及約7.54重量%銀。此焊料組成物之熔點或溫度(液相線)為約140.64℃且固相線為約129.24℃。 This test is carried out in accordance with DIN EN ISO 16750-4-H section 5.4.2. The test samples were 5 12" x 12" tempered glass panels each with 30 power connectors. The board is 4mm thick, dyed, printed in enamel and overprinted with six 1" wide silver strips. The power connector is soldered to the silver strip. The power connectors on both boards are soldered with a solder composition consisting essentially of : about 14.05 wt% tin, about 0.98 wt% bismuth, about 0.87 wt% copper, about 0.70 wt% nickel, about 0.63 wt% zinc, about 74.74 wt% indium, and about 7.78 wt% silver. The melting point of this solder composition or The temperature (liquidus) is about 133.18 ° C and the solidus line is about 123.94 ° C. The power connector on the other board is soldered with a solder composition consisting essentially of: about 14.14 wt% tin, about 0.76 wt% 锑, About 0.64% by weight of copper, about 2.24% by weight of nickel, about 0.75% by weight of zinc, about 76.07% by weight of indium, and about 5.81% by weight of silver. The melting point or temperature (liquidus) of the solder composition is about 137.58 ° C and the solid phase The wire is about 125.92 ° C. The power connector on the other board is soldered with a solder composition consisting essentially of: about 13.43 wt% tin, about 1.31 wt% bismuth, about 0.94 wt% copper, about 2.65 wt% nickel, about 0.49 wt% zinc, about 72.97 wt% indium, and about 7.54 wt% silver. The melting point of this solder composition Or the temperature (liquidus) is about 140.64 ° C and the solidus line is about 129.24 ° C.

在此測試中，一個循環由以下組成：在氣候控制室中將樣品加熱至105℃並持續1小時，其中無電負載或機械負載，隨後將樣品完全浸沒於冷水(約23℃或更低，來自冰箱)中。在每次循環之後用壓縮空氣乾燥樣品。在5個循環之後及隨後在10個循環之後，如圖8中所示且如上所述(在環境溫度下)在數位測力計(Mark-10 Long Island,NY，型號BG100)上將各電力連接器牽拉至50N之力並持續3秒。在此測試期間未發生故障(亦即連接器斷開)。 In this test, one cycle consisted of heating the sample to 105 ° C in the climate control chamber for 1 hour with no electrical or mechanical load, and then completely immersing the sample in cold water (about 23 ° C or lower, from In the refrigerator). Dry with compressed air after each cycle Dry sample. After 5 cycles and then after 10 cycles, each power is placed on a digital dynamometer (Mark-10 Long Island, NY, model BG100) as shown in Figure 8 and as described above (at ambient temperature) The connector is pulled to a force of 50 N for 3 seconds. No faults occurred during this test (ie, the connector was disconnected).

VI.高濕度測試；恆定氣候 VI. High humidity test; constant climate

在此測試中，根據DIN EN ISO 6270-2-CH進行，將8個前窗樣品在環境室中曝露於80℃之恆定溫度及>96% RH之濕度(生成蒸汽)並持續總共504小時，且在達到規定溫度及濕度之後10小時開始在電力連接器上施加14V之電流負載(圖示約22A)並持續15分鐘，且在此後每24小時持續15分鐘直至504小時結束。電力連接器之溫度(利用熱電偶量測)在測試期間因所施加之電負載而增加至約95℃之最大值。在504小時結束之後，如圖8中所示且如上所述(在環境溫度下)在數位測力計(Mark-10 Long Island,NY，型號BG100)上將各電力連接器牽拉至50N之力並持續3秒。若銀層(電接點表面16)在504小時期間或在拉力測試期間與玻璃10分離，則不能進行拉力測試及電測試，且焊料接點被評估為良好。然而，以上在測試V中所述的三個焊料組成物各自有一個前窗樣品完成高濕度/恆定氣候測試且未發生故障(亦即連接器斷開)。 In this test, according to DIN EN ISO 6270-2-CH, 8 front window samples were exposed to a constant temperature of 80 ° C and a humidity of >96% RH (to generate steam) in the environmental chamber for a total of 504 hours. And a current load of 14 V (about 22 A for illustration) was applied to the power connector 10 hours after reaching the specified temperature and humidity for 15 minutes, and thereafter every 15 hours for 15 minutes until the end of 504 hours. The temperature of the power connector (measured by thermocouple) increased to a maximum of about 95 °C during the test due to the applied electrical load. After the end of 504 hours, each power connector was pulled to 50N on a digital dynamometer (Mark-10 Long Island, NY, model BG100) as shown in Figure 8 and as described above (at ambient temperature) Force for 3 seconds. If the silver layer (electrical contact surface 16) is separated from the glass 10 during 504 hours or during the tensile test, tensile testing and electrical testing are not possible and the solder joints are evaluated as good. However, each of the three solder compositions described above in Test V had a front window sample to complete the high humidity/constant climate test without failure (ie, the connector was broken).

VII.耐擋風玻璃清洗劑流體性 VII. Windshield cleaner fluidity

測試樣品為各具有30個電力連接器之12"×12"玻璃板(如上所述)，該等電力連接器用基本上由以下組成之焊料組成物焊接：約14.05重量%錫、約0.98重量%銻、約0.87重量%銅、約0.70重量%鎳、約0.63重量%鋅、約74.74重量%銦及約7.98重量%銀。此焊料組成物之熔點或溫度 (液相線)為約133.18℃且固相線為約123.94℃。 The test samples were 12" x 12" glass plates (described above) each having 30 power connectors soldered with a solder composition consisting essentially of: about 14.05 wt% tin, about 0.98 wt%.锑, about 0.87 wt% copper, about 0.70 wt% nickel, about 0.63 wt% zinc, about 74.74 wt% indium, and about 7.78 wt% silver. The melting point or temperature of this solder composition (Liquid line) was about 133.18 ° C and the solidus line was about 123.94 ° C.

在此測試中，測試樣品浸沒於模擬前窗清洗劑溶液中24小時，該前窗清洗劑溶液由以下製成：11又1/8杯水、3又1/6杯乙醇、1.6杯異丙醇、1又1/4湯匙乙二醇及四分之一湯匙十二烷基硫酸鈉。在24小時結束之後，如圖8中所示且如上所述(在環境溫度下)牽拉各電力連接器，例外為測力計310為以100mm/min之速率在測力計上操作至50N之力並持續2秒的Instron測力計(Instron,Norwood,MA型號5544)。在此測試期間未發生故障(亦即連接器斷開)。 In this test, the test sample was immersed in the simulated front window cleaner solution for 24 hours. The front window cleaner solution is prepared from 11 1/8 cup water, 3 1/6 cup ethanol, 1.6 cup isopropyl alcohol, 1 1/4 tablespoon ethylene glycol, and a quarter spoon. Sodium dodecyl sulfate. After the end of 24 hours, each power connector was pulled as shown in Figure 8 and as described above (at ambient temperature), with the exception that the load cell 310 was operated on a dynamometer to a 50 N at a rate of 100 mm/min. Force and last 2 seconds of Instron dynamometer (Instron, Norwood, MA model 5544). No faults occurred during this test (ie, the connector was disconnected).

VII.鹽霧測試 VII. Salt spray test

此測試根據DIN EN ISO 9227章節8進行。測試樣品為各具有(如上所述)30個電力連接器之12"×12"玻璃板，該等電力連接器用基本上由以下組成之焊料組成物焊接：約14.05重量%錫、約0.98重量%銻、約0.87重量%銅、約0.70重量%鎳、約0.63重量%鋅、約74.74重量%銦及約7.98重量%銀。此焊料組成物之熔點或溫度(液相線)為約133.18℃且固相線為約123.94℃。 This test is carried out in accordance with DIN EN ISO 9227 section 8. The test samples were 12" x 12" glass plates each having (as described above) 30 power connectors soldered with a solder composition consisting essentially of: about 14.05 wt% tin, about 0.98 wt%锑, about 0.87 wt% copper, about 0.70 wt% nickel, about 0.63 wt% zinc, about 74.74 wt% indium, and about 7.78 wt% silver. The melting point or temperature (liquidus) of this solder composition was about 133.18 ° C and the solidus line was about 123.94 ° C.

在此測試中，使測試樣品在測試室(Harshaw型號22)中曝露於鹽噴霧下96小時。鹽濃度為5%且pH值在6.5與7.2之間。鹽霧溫度設定為+35℃±2℃，且塔溫度設定為+48℃，其中空氣壓力在16磅/平方吋(psi)與18磅/平方吋之間。在96小時結束之後，如圖8中所示且如上所述(在環境溫度下)牽拉各電力連接器，例外為測力計310為以100mm/min之速率操作至50N之力並持續2秒的Instron測力計(Instron,Norwood,MA型號5544)。在此測試期間未發生故障(亦即連接器斷開)。 In this test, test samples were exposed to a salt spray for 96 hours in a test chamber (Harshaw Model 22). The salt concentration is 5% and the pH is between 6.5 and 7.2. The salt spray temperature was set to +35 °C ± 2 °C and the column temperature was set to +48 °C with air pressure between 16 psi and 18 psi. After the end of 96 hours, each power connector was pulled as shown in Figure 8 and as described above (at ambient temperature), with the exception that the load cell 310 was operated at a rate of 100 mm/min to a force of 50 N and continued for 2 Seconds of Instron dynamometer (Instron, Norwood, MA Model 5544). No faults occurred during this test (ie, the connector was disconnected).

本文中所引用之所有專利、公開申請案及參考文獻之教示均以其全文引用的方式併入本文中。 The teachings of all patents, published applications and references cited herein are hereby incorporated by reference in their entirety.

雖然本發明已參照其例示具體實例特定展示及描述，但熟習此項技術者應瞭解，在不脫離由隨附申請專利範圍涵蓋的本發明之範疇之情況下，可在其中進行形式及細節之各種改變。 While the invention has been shown and described with reference to the specific embodiments of the present invention, it will be understood by those skilled in the art Various changes.

Claims

一種形成焊料組成物之方法，其包含以下步驟：將銦、鎳、銅、銀、銻及錫熔融；且將使有效形成包括以下之合金之量的該銦、鎳、銅、銀、銻及錫混合在一起：約4重量%至約25重量%錫；約0.1重量%至約8重量%銻；約0.03重量%至約4重量%銅；約0.03重量%至約4重量%鎳；約66重量%至約90重量%銦；及約0.5重量%至約9重量%銀。 A method of forming a solder composition, comprising the steps of: melting indium, nickel, copper, silver, antimony, and tin; and causing effective formation of the indium, nickel, copper, silver, antimony, and Tin is mixed together: from about 4% by weight to about 25% by weight tin; from about 0.1% by weight to about 8% by weight bismuth; from about 0.03% by weight to about 4% by weight copper; from about 0.03% by weight to about 4% by weight nickel; 66% by weight to about 90% by weight of indium; and about 0.5% by weight to about 9% by weight of silver.

如申請專利範圍第1項之方法，其另外包含以下步驟：將該銦與錫一起混合形成第一熔融混合物；將至少該鎳、銅及銀於溶液中一起混合形成第二熔融混合物；且隨後將該第二熔融混合物添加至該第一熔融混合物中。 The method of claim 1, further comprising the steps of: mixing the indium with tin to form a first molten mixture; mixing at least the nickel, copper and silver together in a solution to form a second molten mixture; and subsequently The second molten mixture is added to the first molten mixture.

如申請專利範圍第1項之方法，其另外包含以下步驟：將錫與鎳一起混合形成熔融混合物，且隨後將至少銅、銦及銀添加至該熔融混合物中。 The method of claim 1, further comprising the steps of: mixing tin with nickel to form a molten mixture, and then adding at least copper, indium, and silver to the molten mixture.

如申請專利範圍第3項之方法，其另外包括在所有其他金屬已添加至該熔融混合物中之後將鋅添加至該熔融混合物中的步驟。 The method of claim 3, further comprising the step of adding zinc to the molten mixture after all other metals have been added to the molten mixture.

如申請專利範圍第1項之方法，其中該合金包括約0.2重量%至約8重量%銻。 The method of claim 1, wherein the alloy comprises from about 0.2% by weight to about 8% by weight bismuth.

如申請專利範圍第1項之方法，其中該合金包括約1重量%至約7重量%銀。 The method of claim 1, wherein the alloy comprises from about 1% by weight to about 7% by weight silver.

如申請專利範圍第6項之方法，其中該合金包括約3重量%至約7重量%銀。 The method of claim 6, wherein the alloy comprises from about 3% by weight to about 7% by weight silver.

如申請專利範圍第6項之方法，其中該合金包括約1重量%至約4重量%銀。 The method of claim 6, wherein the alloy comprises from about 1% to about 4% by weight silver.

如申請專利範圍第1項之方法，其另外包括混合約0.2重量%至約6重量%鋅。 The method of claim 1, further comprising mixing from about 0.2% to about 6% by weight zinc.

如申請專利範圍第9項之方法，其中該合金包括約0.3重量%至約6重量%鋅。 The method of claim 9, wherein the alloy comprises from about 0.3% to about 6% by weight zinc.

如申請專利範圍第10項之方法，其中該合金包括約3重量%至約5重量%鋅。 The method of claim 10, wherein the alloy comprises from about 3% by weight to about 5% by weight zinc.

如申請專利範圍第1項之方法，其另外包括混合約0.01重量%至約0.3重量%鍺。 The method of claim 1, further comprising mixing from about 0.01% to about 0.3% by weight of ruthenium.

如申請專利範圍第12項之方法，其中該合金包括約70重量%至約86重量%銦。 The method of claim 12, wherein the alloy comprises from about 70% by weight to about 86% by weight indium.

如申請專利範圍第1項之方法，其中該合金具有範圍在介於約120℃和約145℃之間的固相線溫度。 The method of claim 1, wherein the alloy has a solidus temperature ranging between about 120 ° C and about 145 ° C.

如申請專利範圍第1項之方法，其中該合金具有範圍在介於130℃和約155℃之間的液相線溫度。 The method of claim 1, wherein the alloy has a liquidus temperature ranging between 130 ° C and about 155 ° C.

如申請專利範圍第1項之方法，其中錫以約7重量%至約19重量%之比例混合、銻以約0.2重量%至約8重量%之比例混合、銅以約0.1重量 %至約1.5重量%之比例混合、鎳以約0.1重量%至約4重量%之比例混合、銦以約70重量%至約80重量%之比例混合且銀以約4重量%至約8重量%之比例混合。 The method of claim 1, wherein the tin is mixed in a ratio of about 7% by weight to about 19% by weight, the cerium is mixed in a ratio of about 0.2% by weight to about 8% by weight, and the copper is added in an amount of about 0.1% by weight. Mixing from % to about 1.5% by weight, nickel in a ratio of from about 0.1% by weight to about 4% by weight, indium in a ratio of from about 70% by weight to about 80% by weight, and silver in an amount of from about 4% by weight to about 8% by weight The ratio of % is mixed.

如申請專利範圍第16項之方法，其中該合金包括約74重量%至約78重量%銦。 The method of claim 16, wherein the alloy comprises from about 74% by weight to about 78% by weight indium.

如申請專利範圍第17項之方法，其中該合金包括約5重量%至約10重量%錫。 The method of claim 17, wherein the alloy comprises from about 5% by weight to about 10% by weight tin.

如申請專利範圍第17項之方法，其中該合金包括約12重量%至約19重量%錫。 The method of claim 17, wherein the alloy comprises from about 12% to about 19% by weight tin.

如申請專利範圍第19項之方法，其中該合金包括約12重量%至約16重量%錫。 The method of claim 19, wherein the alloy comprises from about 12% to about 16% by weight tin.

如申請專利範圍第16項之方法，其中該合金包括約74重量%至約80重量%銦。 The method of claim 16, wherein the alloy comprises from about 74% by weight to about 80% by weight indium.

如申請專利範圍第16項之方法，其中該合金包括約0.1重量%至約3重量%鎳。 The method of claim 16, wherein the alloy comprises from about 0.1% to about 3% by weight nickel.

如申請專利範圍第16項之方法，其中該合金包括約0.2重量%至約5重量%銻。 The method of claim 16, wherein the alloy comprises from about 0.2% by weight to about 5% by weight bismuth.

如申請專利範圍第1項之方法，其中該合金包括：約4重量%至約20重量%錫；約0.1重量%至約8重量%銻；約0.1重量%至約4重量%銅；約0.1重量%至約3重量%鎳；約71重量%至約86重量%銦；及約1重量%至約6重量%銀。 The method of claim 1, wherein the alloy comprises: from about 4% by weight to about 20% by weight tin; from about 0.1% by weight to about 8% by weight bismuth; from about 0.1% by weight to about 4% by weight copper; about 0.1% % by weight to about 3% by weight of nickel; From about 71% by weight to about 86% by weight indium; and from about 1% by weight to about 6% by weight silver.

如申請專利範圍第24項之方法，其中該合金包括約10重量%至約19重量%錫。 The method of claim 24, wherein the alloy comprises from about 10% by weight to about 19% by weight tin.

如申請專利範圍第24項之方法，其中該合金包括約74重量%至約80重量%銦。 The method of claim 24, wherein the alloy comprises from about 74% by weight to about 80% by weight indium.

如申請專利範圍第26項之方法，其中該合金包括約1重量%至約7重量%銀。 The method of claim 26, wherein the alloy comprises from about 1% to about 7% by weight silver.

如申請專利範圍第27項之方法，其中該合金包括約3.5重量%銅。 The method of claim 27, wherein the alloy comprises about 3.5% by weight copper.

如申請專利範圍第24項之方法，其中該合金包括約0.1重量%至約1重量%鎳。 The method of claim 24, wherein the alloy comprises from about 0.1% by weight to about 1% by weight nickel.

如申請專利範圍第24項之方法，其中該合金包括約1重量%至約2重量%鎳。 The method of claim 24, wherein the alloy comprises from about 1% by weight to about 2% by weight nickel.

如申請專利範圍第24項之方法，其中該合金包括約0.2重量%至約2重量%銻。 The method of claim 24, wherein the alloy comprises from about 0.2% by weight to about 2% by weight bismuth.

如申請專利範圍第24項之方法，其中該合金包括約2重量%至約6重量%銻。 The method of claim 24, wherein the alloy comprises from about 2% to about 6% by weight bismuth.

一種形成焊料組成物之方法，其包含以下步驟：將銦、鎳、銅、銀、銻及錫熔融；且將使有效形成包括以下之合金之量的該銦、鎳、銅、鋅、銀、銻及錫混合在一起：約11重量%至約17重量%錫；約0.5重量%至約3重量%銻；約0.5重量%至約1.5重量%銅；約0.5重量%至約5重量%鎳；約72重量%至約77重量%銦；約4重量%至約8.5重量%銀；及約0.3重量%至約1.5重量%鋅。 A method of forming a solder composition, comprising the steps of: melting indium, nickel, copper, silver, antimony, and tin; and in an amount effective to form an indium, nickel, copper, zinc, silver, Mixing tin and tin together: about 11% by weight to about 17% by weight tin; From about 0.5% by weight to about 3% by weight bismuth; from about 0.5% by weight to about 1.5% by weight copper; from about 0.5% by weight to about 5% by weight nickel; from about 72% by weight to about 77% by weight of indium; about 4% by weight to about 8.5 wt% silver; and from about 0.3 wt% to about 1.5 wt% zinc.

如申請專利範圍第33項之方法，其中該合金包括：約13重量%至約15重量%錫；約0.5重量%至約2.5重量%銻；約0.5重量%至約1.5重量%銅；約1重量%至約4重量%鎳；約74重量%至約75重量%銦；約5重量%至約6重量%銀；及約0.5重量%至約1.5重量%鋅。 The method of claim 33, wherein the alloy comprises: from about 13% by weight to about 15% by weight tin; from about 0.5% by weight to about 2.5% by weight bismuth; from about 0.5% by weight to about 1.5% by weight copper; about 1 From wt% to about 4 wt% nickel; from about 74 wt% to about 75 wt% indium; from about 5 wt% to about 6 wt% silver; and from about 0.5 wt% to about 1.5 wt% zinc.

如申請專利範圍第34項之方法，其中該合金包括：約15重量%錫；約0.5重量%至約1.5重量%銻；約0.5重量%至約1.5重量%銅；約1重量%鎳；約75重量%銦；約6重量%銀；及約0.5重量%至約1.5重量%鋅。 The method of claim 34, wherein the alloy comprises: about 15% by weight tin; about 0.5% by weight to about 1.5% by weight bismuth; about 0.5% by weight to about 1.5% by weight copper; about 1% by weight nickel; 75 wt% indium; about 6 wt% silver; and about 0.5 wt% to about 1.5 wt% zinc.

如申請專利範圍第35項之方法，其中該合金包括：約15重量%錫；約1重量%銻；約1重量%銅；約1重量%鎳；約75重量%銦；約6重量%銀；及約1重量%鋅。 The method of claim 35, wherein the alloy comprises: about 15% by weight tin; about 1% by weight bismuth; about 1% by weight copper; about 1% by weight nickel; about 75% by weight indium; about 6% by weight silver And about 1% by weight of zinc.

如申請專利範圍第33項之方法，其中該合金包括：約14重量%錫；約0.5重量%至約1.5重量%銻；約0.5重量%至約1.5重量%銅；約3重量%鎳；約75重量%銦；約5重量%銀；及約0.5重量%至約1.5重量%鋅。 The method of claim 33, wherein the alloy comprises: about 14% by weight tin; about 0.5% by weight to about 1.5% by weight bismuth; about 0.5% by weight to about 1.5% by weight copper; about 3% by weight nickel; 75 wt% indium; about 5 wt% silver; and about 0.5 wt% to about 1.5 wt% zinc.

如申請專利範圍第37項之方法，其中該合金包括：約14重量%錫；約1重量%銻；約1重量%銅；約3重量%鎳；約75重量%銦；約5重量%銀；及約1重量%鋅。 The method of claim 37, wherein the alloy comprises: about 14% by weight tin; about 1% by weight bismuth; about 1% by weight copper; about 3% by weight nickel; about 75% by weight indium; About 5% by weight of silver; and about 1% by weight of zinc.

如申請專利範圍第34項之方法，其中該合金包括：約13重量%錫；約1.5重量%至約2.5重量%銻；約1.5重量%至約1.5重量%銅；約4重量%鎳；約74重量%銦；約5重量%銀；及約0.5重量%至約1.5重量%鋅。 The method of claim 34, wherein the alloy comprises: about 13% by weight tin; about 1.5% by weight to about 2.5% by weight bismuth; about 1.5% by weight to about 1.5% by weight copper; about 4% by weight nickel; 74% by weight of indium; about 5% by weight of silver; and about 0.5% by weight to about 1.5% by weight of zinc.

如申請專利範圍第39項之方法，其中該合金包括：約13重量%錫；約2重量%銻；約1重量%銅；約4重量%鎳；約74重量%銦；約5重量%銀；及約1重量%鋅。 The method of claim 39, wherein the alloy comprises: about 13% by weight tin; about 2% by weight bismuth; about 1% by weight copper; about 4% by weight nickel; about 74% by weight indium; about 5% by weight silver And about 1% by weight of zinc.